CN100427319C - Dispersion composition and recording material - Google Patents

Dispersion composition and recording material Download PDF

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CN100427319C
CN100427319C CNB2004800311749A CN200480031174A CN100427319C CN 100427319 C CN100427319 C CN 100427319C CN B2004800311749 A CNB2004800311749 A CN B2004800311749A CN 200480031174 A CN200480031174 A CN 200480031174A CN 100427319 C CN100427319 C CN 100427319C
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composition
dispersion
dispersion liquid
whiteness
addition
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CN1871132A (en
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长泽俊明
富田忍
河野哲史
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Chemipro Kasei Kaisha Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

A dispersion composition containing a urea-urethane (UU) compound as (a) component, and one or more types of coloring inhibitors selected from among a silicate, a carbonate, a sulfate, a phosphate, a metal oxide, a metal hydroxide, a hindered phenol compound, a hindered amine compound and an acetoacetic acid derivative as (b) component, characterized in that one or more components selected from (a) component and (b) component is subjected to a heating treatment, or a developer UU dispersion prepared by using a cellulose derivative and a specific anionic surfactant as a dispersant for the developer UU is subjected to a heating treatment. The above dispersion composition containing a urea-urethane compound allows the improvement of the phenomenon of the lowering with time of the whiteness of an application fluid containing a colorless or pale dye precursor and a urea-urethane compound, and also allow the improvement of the discoloration of a white portion, in particular, the discoloration under a high humidity condition (the resistance to wet discoloration of a white portion) of a thermal recording material manufactured by the use of said application fluid.

Description

Dispersion composition and recording materials
Technical field
The present invention relates to contain the dispersion composition of urea-carbamate compounds, it is used to contain colourless or light dyestuff former and (a) preparation of the temperature-sensitive developer coating liquid of urea-carbamate compounds.
Background technology
Up to now, known have a multiple chemical colour reaction system that has used record energy such as heat, pressure.Wherein, what know already is usually by colourless or light dyestuff former be used for contact with this dyestuff former the Color Appearance System that 2 composition color development system of the developer of colour developing constitute, and representative example can be enumerated: the thermal recording medium of the pressure sensitive recording material of working pressure energy, use thermal energy, the photosensitive recording material of use light energy etc.
In recent years, in the information equipments that make preparations for sowing such as facsimile machine, printing machine, logger, adopt the thermal photography mode of utilizing thermal energy to write down mostly.These thermal recording mediums possess whiteness height, outward appearance, feel near multiple good characteristics such as record adaptability such as common paper, developing sensitivity are good, in addition, thermal photography has equipment miniaturization, Maintenance free, do not have advantage such as noise, is widely used in metering with fields such as automatic machine such as recorder, facsimile machine, printing machine, computer terminal, label, ticket.Wherein, use the thermal photography of the such acid developer of colourless or light electron donability dyestuff former (particularly leuco dye) and phenoloid as developer, reactive high as the dyestuff former of this electron donability compound, by contacting, can obtain the colour developing image of high concentration thus moment with developer as electronic acceptance compound.But, there is following shortcoming on the contrary: because the chemical resistance of the colour developing image of the recording section that obtains is poor, therefore, the medicine that contains in plasticizer that contains in contact plastic sheet and the rubber or the foods and cosmetics, record evanescence, in addition, because its light resistance is poor, therefore, the daylight of short time exposes record and will fade, even disappearance etc., the record storage stability is poor.
In order to adapt to these requirements, urea-carbamate compounds class developer (below be designated as developer UU) (for example patent documentation 1) has been proposed.This developer UU has the excellent images keeping quality, on the other hand, its sensitivity is insufficient, therefore, when being used for the highly sensitive purposes of requirement, must use 2 simultaneously, two (4-hydroxy phenyl) propane of 2-(below be designated as BPA), two (4-hydroxy phenyl) sulfone (below be designated as BPS), 4-isopropyl oxygen base phenyl-4 '-hydroxy phenyl sulfone (below be designated as D-8), 2, the general developers of high sensitivity such as 4 '-dihydroxydiphenylsulisomer (below be designated as 2,4 ' BPS).
But, there are the following problems with coating liquid for the thermal recording medium that contains colourless or light dyestuff former and developer UU: pass in time that produce painted causes that whiteness descends in (liquid photographic fog), painted (background fog) of the white portion by applying the electrothermal sensitive recording paper that its coating liquid is made, electrothermal sensitive recording paper is kept at the heat-sensitive paper that high humidity following time takes place painted (the moisture-proof background fog) of white portion obvious, when using the general developers of high sensitivity such as D-8 simultaneously, liquid photographic fog, moisture-proof background fog can be more obvious.
[patent documentation 1] international publication number WO00/14058 (EP1116713A1)
Summary of the invention
The objective of the invention is to, dispersion composition is provided, it contains thermal recording medium developer UU, can improve painted (background fog) of decline (liquid photographic fog) that the thermal recording medium that contains colourless or light dyestuff former and developer UU passes in time with the whiteness of coating liquid and the white portion by applying the electrothermal sensitive recording paper that this coating liquid is made, electrothermal sensitive recording paper is kept at painted (the moisture-proof background fog) of white portion of the heat-sensitive paper of high humidity generation of following time, it is good to print sensitivity simultaneously.
The present inventor is in order to solve above-mentioned problem, study repeatedly without single devotion, found that, for containing as the urea-carbamate compounds of (a) composition and (for example: silicate as the painted inhibitor of (b) composition, carbonate, sulfate, phosphate, metal oxide, metal hydroxides, hindered phenol compound, hindered amine compound, acetoacetate derivative etc.) dispersion composition, by at least a heat treated of carrying out to the composition dispersion liquid that constitutes this dispersion composition, perhaps use as the cellulose derivative of the dispersant of developer UU and specific anion surfactant and disperse, and the developer UU dispersion liquid that obtains carried out heat treated, can realize above-mentioned purpose, thereby finish the present invention.
That is, the invention provides composition, it is by will being scattered in the liquid medium as at least a compound that has at least one urea groups and at least one carbamate groups in a part respectively of (a) composition, and (a) composition was carried out heat treated obtains.
In addition, the invention provides composition, the urea-carbamate compounds of wherein aforementioned (a) composition is at least a in the material of any expression of following general formula (I)～(VI).
Figure C20048003117400101
(wherein, X, Y, Z represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and in addition, each residue can have substituting group);
Figure C20048003117400102
(wherein, X, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and in addition, each residue can have substituting group);
(wherein, X, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and α represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer, and in addition, each residue can have substituting group);
Figure C20048003117400104
(wherein, Z, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and β represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer, and in addition, each residue can have substituting group);
Figure C20048003117400111
(wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue, and in addition, each residue can have substituting group; γ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-, following formula (a) any or represent direct key, n is 1 or 2);
Figure C20048003117400112
(wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue, and in addition, each residue can have substituting group; δ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-,-NH-,-CH (COOR 1)-,-C (CF 3) 2-,-CR 2R 3-any or represent direct key, wherein, R 1, R 2, R 3The expression carbon number is 1 to 20 alkyl, and n is 1 or 2).
In addition, the invention provides composition, wherein in foregoing, contain: the urea-carbamate compounds of aforementioned (a) composition is scattered in the liquid medium, heats available dispersion liquid being not less than under 40 ℃ the temperature.
In addition, the invention provides temperature-sensitive Color Appearance System preparation compositions, it contains: be scattered in the dispersion liquid that forms in the liquid medium with the urea-carbamate compounds of aforementioned (a) composition and as at least a compound that is selected from silicate, carbonate, sulfate, phosphate, metal oxide, metal hydroxides, hindered phenol compound, hindered amine compound and the acetoacetate derivative of (b) painted inhibitor composition.
In addition, the invention provides and contain aforementioned (a) composition and (b) composition of painted inhibitor composition, the either party by aforementioned at least (a) and (b) composition carries out heat treated and can obtain.
In addition, the invention provides and contain aforementioned (a) composition and (b) composition of painted inhibitor composition, wherein urea-the carbamate compounds of (a) composition is at least a in the material of any expression of above-mentioned general formula (I)～(VI).
In addition, the invention provides and contain aforementioned (a) composition and (b) composition of painted inhibitor composition, wherein aforementioned (b) composition is to be selected from magnesium silicate, calcium silicates, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium phosphate, 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) sodium phosphate, magnesia, aluminium oxide, titanium oxide, magnesium hydroxide, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl group base phenyl) butane, three (2, the 6-dimethyl-4-tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester, acetoacetanilide, acetoacetyl is for meta-xylene amine, with at least a in the adjacent methylamine of acetoacetyl.
In addition, the invention provides foregoing, it further contains: be selected from phenol derivatives, aromatic derivant carboxylate or its metal salt compound, salicyclic acid derivatives or its metal salt compound, N, at least a compound in N-diaryl thiourea derivative and the sulfonyl urea derivates as (c) acid developer composition.
In addition, the invention provides composition, the phenol derivatives of wherein aforementioned (c) composition is to be selected from 2, two (4-hydroxy phenyl) propane of 2-, two (4-hydroxy phenyl) sulfone, 4-isopropyl oxygen base phenyl-4 '-hydroxy phenyl sulfone, 2, at least a in 4 '-dihydroxydiphenylsulisomer, two (3-pi-allyl-4-hydroxy phenyl) sulfone and the 4-Para Hydroxy Benzoic Acid benzyl ester.
In addition, the invention provides and contain aforementioned (a) composition and (b) composition of composition and as required (c) composition, it contains and aforementioned (a) composition is scattered in the liquid medium and heats available dispersion liquid being not less than under 40 ℃ the temperature.
In addition, the invention provides and contain aforementioned (a) composition and (b) composition of composition and as required (c) composition, it contains and aforementioned (b) composition is scattered in the liquid medium and heats available dispersion liquid being not less than under 40 ℃ the temperature.
In addition, the invention provides and contain aforementioned (a) composition and (b) composition of composition and as required (c) composition, it contains and aforementioned (a) composition is scattered in the liquid medium and heats available dispersion liquid under being not less than 40 ℃ temperature, and being scattered in (b) composition in the liquid medium and being not less than under 40 ℃ the temperature and heat available dispersion liquid.
In addition, the invention provides and contain aforementioned (a) composition and (b) composition of composition and as required (c) composition, wherein, with respect to (a) composition (urea-carbamate compounds) 100 mass parts, the amount of aforementioned (b) composition (painted inhibitor) is that 1 mass parts is extremely less than 50 mass parts.
In addition, the invention provides foregoing, wherein, when with described (a) composition (urea-carbamate compounds) and/or (b) composition (painted inhibitor) disperses, use at least a dispersant that is selected from water-soluble nonionic macromolecular compound, water soluble anion macromolecular compound, anion surfactant, non-ionic surface active agent and the zwitterionic surfactant to make its dispersion.
In addition, the invention provides foregoing, wherein, when with described (a) composition (urea-carbamate compounds) and/or (b) composition (painted inhibitor) disperses, use at least a dispersant that is selected from nonionic or the anionic water-soluble macromolecular compound in polyvinyl alcohol derivative and the cellulose derivative and is selected from the anion surfactant to make its dispersion.
In addition, the invention provides foregoing, wherein, when with described (a) composition (urea-carbamate compounds) and/or (b) composition (painted inhibitor) disperses, use the polyvinyl alcohol that is selected from as the sulfonic acid modified of polyvinyl alcohol derivative, as the hydroxypropyl methylcellulose of described cellulose derivative, and make its dispersion as the slaine that is selected from beta-naphthalenesulfonic-acid formaldehyde condensation compound of described anion surfactant and at least a dispersant in poly carboxylic acid derivative's type surfactant.
In addition, the invention provides recording materials, wherein on support, be provided with the color layer that contains foregoing.
In addition, the invention provides thermal recording medium, wherein on support, be provided with the color layer that contains foregoing.
It is still indeterminate to utilize the application's dispersion composition to suppress the painted mechanism of coating liquid, can think to cause because by dispersion liquid is carried out heat treated: (a) atomic inactivation that the reactivity of composition (urea-carbamate compounds) is high or the chromogenic reaction that promotes dispersant to cause to the absorption on dispersed particle surface suppress, cause that by (b) composition (painted inhibitor) chromogenic reaction hinders.In addition, up to now, the occasion that known sensitivity is good causes the liquid photographic fog of coating liquid, the background fog of heat-sensitive paper easily.But, the application's dispersion composition is kept high printing sensitivity, and the liquid photographic fog takes place, the reason of background fog, can think: be since (b) composition (painted inhibitor) suppress to contain (a) composition (urea-carbamate compounds) and (c) the liquid photographic fog that mainly causes by (a) composition (urea-carbamate compounds) of the dispersion composition of composition (acid developer) and the chromogenic reaction of moisture-proof background fog, in case but when the particle heat fusing of developer UU, (b) composition (painted inhibitor) is to the unencumbered cause of chromogenic reaction of dyestuff and developer UU.As the dispersant that can give such function, in the polyvinyl alcohol of cellulose derivative, sulfonic acid modified, anion surfactant, slaine, poly carboxylic acid derivative's type surfactant of preferred naphthalene sulfonic acid-formaldehyde condensation product.
The present invention is more preferably: contain in use (a) composition (urea-carbamate compounds) and (b) thermal recording medium of the dispersion composition preparation of composition (painted inhibitor) with in the coating liquid, by to as (a) composition (urea-carbamate compounds) of the constituent of dispersion composition and (b) at least a heat treated of carrying out of the dispersion liquid of composition (painted inhibitor), perhaps use cellulose derivative and specific anion surfactant to disperse as the dispersant of developer UU, dispersion liquid to the developer UU that obtains carries out heat treated, suppress the decline (liquid photographic fog) that the whiteness of coating liquid is passed in time thus, and be greatly improved, and has the effect that can manifest high printing sensitivity by applying the background fog (moisture-proof background fog) of thermal recording medium under high humidity that this coating liquid is made.
In addition, by using and (for example with the highly sensitive general developer of the dispersion liquid of (a) composition (urea-carbamate compounds) and conduct (c) composition (acid developer), be selected from phenol derivatives, aromatic derivant carboxylate or its metal salt compound, salicyclic acid derivatives or its metal salt compound, N, at least a compound in N-diaryl thiourea derivative and the sulfonyl urea derivates) the coating liquid of the dispersion composition of composition preparation, apply the decline (liquid photographic fog) that the whiteness of liquid passes in time and the background fog (moisture-proof background fog) of thermal recording medium more significantly and also improve greatly, and have the effect that can manifest high printing sensitivity.Like this by suitably selecting the dispersant of (a) composition, can obtain the effect that the inhibition whiteness as purpose descends, by and with (a) composition and (b) composition, can further suppress the decline that the whiteness of coating liquid under the hot conditions is passed in time.
The specific embodiment
Below, preferred implementation of the present invention is elaborated.
(a) of the present invention composition (urea-carbamate compounds) is meant the compound that has at least one urea groups (NHCONH-yl) and at least one carbamate groups (NHCOO-yl) in the molecule respectively.
Urea-carbamate compounds of the present invention, as long as exist urea groups and carbamate groups just passable in the molecule, but the urea-carbamate compounds of any expression of preferred formula (I)～(VI).More preferably aromatic compound or heterocyclic compound.Further preferred: in the molecule except that urea groups and carbamate groups, sulfuryl (SO 2-yl) or anilid base (NHCO-yl) with directly the form of key on urea groups exist.The particulars of these urea-carbamate compounds for example are recorded among the international publication number WO00/14058, can be synthetic according to the method for wherein record.
Urea-the carbamate compounds of (a) composition of any expression of general formula of the present invention (I)～(VI) for example is the compound that obtains according to synthesis example as follows.
Urea-the carbamate compounds of (a) composition of general formula (I) expression, can obtain by the following method: for example, make the isocyanate compound that contains OH based compound and following general formula (VIII) of following general formula (VII) and the amines of following general formula (IX), react according to for example following reaction expression (A).
X-OH (VII)
OCN-Y-NCO (VIII)
Z-NH 2(IX)
(wherein, X, Y, Z represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and in addition, each residue can have substituting group.)
Figure C20048003117400161
Urea-the carbamate compounds of (a) composition of general formula (II) expression, can obtain by the following method: for example, make the isocyanate compound and the water that contain OH based compound and above-mentioned general formula (VIII) of above-mentioned general formula (VII), react according to for example following reaction expression (B).
Figure C20048003117400171
Urea-the carbamate compounds of (a) composition of general formula (III) expression, can obtain by the following method: for example, make the isocyanate compound that contains OH based compound and above-mentioned general formula (VIII) of above-mentioned general formula (VII) and the amines of following general formula (X), react according to for example following reaction expression (C).
Figure C20048003117400172
(wherein, α represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer.)
Figure C20048003117400173
Urea-the carbamate compounds of (a) composition of general formula (IV) expression, can obtain by the following method: for example, what make the isocyanate compound of the amines of above-mentioned general formula (IX) and above-mentioned general formula (VIII) and following general formula (XI) contains the OH based compound, reacts according to for example following reaction expression (D).
Figure C20048003117400174
(wherein, β represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer.)
Urea-the carbamate compounds of (a) composition of general formula (V) expression can obtain by the following method: for example, make the diamine compound of monohydric phenol compound and two isocyanato-phenyl (ジ イ ソ シ ア Na one ト Off エ ニ Le) compound and following general formula (XII), react according to for example following reaction expression (E).
Figure C20048003117400182
(wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue.In addition, each residue can have substituting group.γ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-, following general formula (a) any or represent direct key, n is 1 or 2.)
Figure C20048003117400191
Urea-the carbamate compounds of (a) composition of general formula (VI) expression, can obtain by the following method: for example, make the dihydroxy compounds of anil and two isocyanato-phenyl compounds and following general formula (XIII), react according to for example following reaction expression (F).
Figure C20048003117400192
(wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue.In addition, each residue can have substituting group.δ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-,-NH-,-CH (COOR 1)-,-C (CF 3) 2-,-CR 2R 3-any or represent direct key, R 1, R 2, R 3The expression carbon number is 1 to 20 alkyl, and n is 1 or 2.)
Figure C20048003117400201
In the urea-carbamate compounds of (a) composition of these general formulas (I)～(VI) expressions, preferred formula (II) is to the compound of general formula (IV), the compound of special preferred formula (V).
Urea-the carbamate compounds of (a) of the present invention composition is the colourless or light compound of solid usually at normal temperatures, and molecular weight is preferably and is no more than 5000, further preferably is no more than 2000.In addition, preferably have urea-carbamate compounds one side of fusing point in thermal recording medium, fusing point is preferably 40 ℃～500 ℃, is preferably 60 ℃～300 ℃ scope especially.In the present invention, above-mentioned urea-carbamate compounds at least a, two or more use simultaneously as required the time.
Comprise the preparation method of dispersion composition of the urea-carbamate compounds of (a) composition, be not particularly limited, for example, carry out by the following method.
Urea-the carbamate compounds of (a) composition is pre-dispersed in advance together to the aqueous solution with water soluble polymer and/or anion surfactant with dispersibility, by this pre-dispersed liquid being used as required pulverizers such as coating oscillator (paint shaker), ball mill, vibrator, grater (attritor), puddle mixer, Dyno mill, colloid mill, sand mill be crushed to suitable particle diameter, the dispersion liquid of preparation (a) composition (urea-carbamate compounds) can directly be used it for dispersion composition thus.
The painted inhibitor of (b) composition among the present invention is meant inorganic compound and organic compounds such as ultra-violet absorbers such as hindered phenol compound, hindered amine compound, image preservative agent, fade inhibitor, light stabilizer and acetoacetate derivative such as silicate, carbonate, sulfate, phosphate, metal oxide, metal hydroxides.More specifically, aforementioned inorganic compound for example has: magnesium silicate, alumina silicate, calcium silicates, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium phosphate, aluminum phosphate, calcium phosphate, trbasic zinc phosphate, magnesia, aluminium oxide, zinc oxide, titanium oxide, silicic acid, magnesium hydroxide, aluminium hydroxide, zinc hydroxide etc.In addition, the metal species of salt can be a plurality of, can be for example lithium aluminium silicate, calcium aluminosilicate, calcium silicates sodium, calcium magnesium silicate etc.In addition, also comprise: the aluminosilicate that the part of the silicon of silicate is formed with the aluminium displacement, the silicate ester compound that a part of esterification of silicate is formed, phosphate compound that phosphatic a part of esterification is formed etc.
Wherein, preferred magnesium silicate, calcium silicates, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium phosphate, 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) sodium phosphate, magnesia, aluminium oxide, titanium oxide, magnesium hydroxide.Further preferred magnesium silicate, calcium silicates, magnesium carbonate, calcium carbonate, calcium sulfate, magnesia, magnesium hydroxide.
More specifically; aforementioned organic compound for example has: 1; 1; 3-three (3 '-cyclohexyl-4 '-hydroxy phenyl) butane; 1; 1; 3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; three (2; 6-dimethyl-4-the tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester; 4; 4 '-sulphur two (3 methy 6 tert butyl phenol); 4; 4 '-butylidene two (3-methyl-6-tert butyl phenyl); 1; 3; 5-trimethyl-2; 4; 6-three (3; the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone; OPS p octylphenyl salicylate; 2-(2 '-hydroxyl-5 '-tolyl) BTA; 2-cyano group-3; 3 '-diphenylacrylate ethyl ester; 1; 2,3,4-BTCA four (2; 2; 6,6-tetramethyl-4-piperidyl) ester; 2,2 '-di-2-ethylhexylphosphine oxide (4; the 6-di-tert-butyl-phenyl) sodium phosphite; dodecylic acid two [2-(2-hydroxy benzoyl) hydrazides]; 1; 2,3,4-BTCA four (1; 2; 2,6,6-pentamethyl-4-piperidyl) ester; acetoacetanilide as acetoacetate derivative; acetoacetyl is for ortho-aminotoluene; acetoacetyl is for para-totuidine; acetoacetyl is for meta-xylene amine; acetoacetyl is for o-aminoanisole; acetoacetyl replaces o-chloraniline etc.
Wherein, preferred 1; 1; 3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, three (2, the 6-dimethyl-4-tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester, acetoacetanilide, acetoacetyl are for meta-xylene amine, acetoacetyl ortho-aminotoluene.
Comprise the preparation method of dispersion composition of the painted inhibitor of (b) composition, be not particularly limited, for example can use with the same method of the urea-carbamate compounds of (a) composition and carry out.The painted inhibitor of (b) composition is pre-dispersed in advance together to the aqueous solution with water soluble polymer and/or anion surfactant with dispersibility, by this pre-dispersed liquid is crushed to suitable particle diameter with pulverizers such as coating vibrating machine, ball mill, vibrator, grater, puddle mixer, Dyno grinding machine, colloid mill, sand mills as required, the dispersion liquid of preparation (b) composition (painted inhibitor) can be directly used in dispersion composition with it thus.(b) after composition (painted inhibitor) also can mix with the pre-dispersed liquid that comprises (a) composition (urea-carbamate compounds) at the pre-dispersed liquid with (b) composition (painted inhibitor), pulverize (hereinafter referred to as pulverizing altogether).
Particle diameter as the dispersion liquid of the painted inhibitor of (b) composition is no more than the painted inhibition effect of 100 μ m height owing to be, so preferably.More preferably be no more than 50 μ m, more preferably 0.1 μ m～10 μ m.
Consider from the whiteness decline effect of improvement coating liquid and/or the moisture-proof background fog effect of improvement recording materials, urea-carbamate compounds 100 mass parts with respect to (a) composition, (b) consumption of the painted inhibitor of composition is preferably 1 mass parts extremely less than 50 mass parts, 1 mass parts to 20 mass parts more preferably, even use 50 mass parts or more, it is also little that the further whiteness decline of coating liquid suppresses effect, almost do not see the further effect of improving of the moisture-proof background fog improved effect of electrothermal sensitive recording paper, can confirm that sensitivity descends.
(b) composition (painted inhibitor) can use separately, also can two or more use simultaneously.
The acid developer of (c) composition among the present invention is that normally used electronics is accepted material, preferred phenol derivatives, aromatic derivant carboxylate or its metal salt compound, salicyclic acid derivatives or its metal salt compound, N, N-diaryl thiourea derivative, sulfonyl urea derivates etc.Particularly preferred phenol derivatives concrete example if any: 2, two (4-hydroxy phenyl) propane (BP (A) of 2-, 2, two (hydroxy phenyl) butane of 2-, 2, two (hydroxy phenyl) pentanes of 2-, 2, two (4-the hydroxy phenyl)-4-methylpentanes (AP-5) of 2-, 2, two (hydroxy phenyl) heptane of 2-, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, two (4-hydroxy phenyl) butyl acetate, two (4-hydroxy phenyl) benzyl acetate, two (4-hydroxy phenyl) sulfones (BPS), 2,4 '-dihydroxydiphenylsulisomer (2,4 '-BPS), two (3-methyl-4-hydroxy phenyl) sulfone, 4-hydroxy phenyl-4 '-methyl phenyl sulfone, 3-chloro-4-hydroxy phenyl-4 '-methyl phenyl sulfone, 3,4-dihydroxyphenyl-4 '-methyl phenyl sulfone, 4-isopropyl phenyl-4 '-hydroxy phenyl sulfone, 4-isopropyl oxygen base phenyl-4 '-hydroxy phenyl sulfone (D-8), two (3-pi-allyl-4-hydroxy phenyl) sulfone (TGS (A), 4-hydroxy phenyl-4 '-benzyl oxygen base phenylsulfone, 4-isopropyl phenyl-4 '-hydroxy phenyl sulfone, two (2-methyl-3-tert-butyl-hydroxy phenyl) sulfide, 4-Para Hydroxy Benzoic Acid methyl esters, 4-Para Hydroxy Benzoic Acid benzyl ester, 4-Para Hydroxy Benzoic Acid (4 '-chloro benzyl ester), 1, two (4 '-Para Hydroxy Benzoic Acid) ethyl esters of 2-, 1, two (4 '-Para Hydroxy Benzoic Acid) pentyl esters of 5-, 1, two (4 '-Para Hydroxy Benzoic Acid) the own esters of 6-, 3-hydroxy benzenes two dimethyl phthalates, the hard ester ester of gallic acid, dodecyl gallate etc.Salicyclic acid derivatives for example has: gaultherolin, salethyl, isoamyl salicylate, isoamyl salicylate, phenyl salicytate, benzyl salicylate, 4-n-octyloxy salicylic acid, 4-n-butoxy salicylic acid, 4-n-pentyloxy salicylic acid, 3-n-dodecane oxygen base salicylic acid, the positive hot acyloxy salicylic acid of 3-, 4-n-octyl oxygen carbonylamino salicylic acid, the positive hot acyloxy carbonylamino salicylic acid of 4-, salicylamide, salicylaniline etc.In addition, sulfonyl urea derivates for example 4, two (tolysulfonyl amino carbonyl amino) diphenyl-methanes, 4 of 4-, two (the adjacent tosyl amino carbonyl amino) diphenyl-methanes, 4 of 4-, two (tolysulfonyl amino carbonyl amino) diphenylsulfide, 4 of 4-, the compound that contains at least one Arenesulfonyl amino urea groups of two (tolysulfonyl amino carbonyl amino) diphenyl ethers of 4-, N-(tolysulfonyl)-N '-phenylurea etc.
Wherein, be preferably selected from 2,2-two (4-hydroxy phenyl) propane (BP (A), two (4-hydroxy phenyl) sulfones (BPS), 2,4 '-dihydroxydiphenylsulisomer (2,4 '-BPS), 4-isopropyl oxygen base phenyl-4 '-hydroxy phenyl sulfone (D-8), two (3-pi-allyl-4-hydroxy phenyl) sulfone (TGS (A), 2, the compound in two (4-the hydroxy phenyl)-4-methylpentanes (AP-5) of 2-, the 4-Para Hydroxy Benzoic Acid benzyl ester.
With respect to colourless or light dyestuff former, preferred above-mentioned acid developer uses with the ratio of 5～500 quality %, more preferably 20～300 quality %.Acid developer is 5 quality % or more for a long time, the colour developing of dyestuff former is good, and colour developing concentration is also high.In addition, acid developer is 500 quality % or still less the time, acid developer is difficult to residual, and is also favourable economically, so preferred.
Comprise the preparation method of dispersion composition of the acid developer of (c) composition, be not particularly limited, for example can use with the same method of the dispersion composition of (a) composition (urea-carbamate compounds) to be prepared.
That is, with (c) composition (acid developer) with to have the water soluble polymer and/or an anion surfactant of dispersibility pre-dispersed in advance together to the aqueous solution, by this pre-dispersed liquid is crushed to suitable particle diameter with pulverizers such as coating vibrating machine, ball mill, vibrator, grater, puddle mixer, Dyno mill, colloid mill, sand mills as required, the dispersion liquid of preparation (c) composition (acid developer) can be directly used in dispersion composition with it thus.
The following describes to the urea-carbamate compounds of (a) composition and (b) composition painted inhibitor independent dispersion liquid or mixed dispersion liquid composition carry out heat treated respectively.
(a) heating treatment method of composition (urea-carbamate compounds) dispersion liquid, be not particularly limited, for example have: the dispersion composition that will comprise the urea-carbamate compounds of (a) composition is packed in the container, on one side with stirrings such as paddle, the method for heating on one side; The method of in the process that the composition that will comprise urea-carbamate compounds is pulverized with pulverizers such as coating vibrating machine, ball mill, vibrator, grater, sand mill, Dyno mill, colloid mill, sand mills, heating; After normal temperature is pulverized, make temperature rising in the container, carry out stirring method etc. then.
(a) condition of the heat treated of the urea of composition-carbamate compounds dispersion liquid was preferably carried out 3 hours at 40 ℃ to 90 ℃ proper temperature at least.Further preferably carried out at least 3 hours, more preferably carried out at least 4 hours at 55 ℃～75 ℃ at 50 ℃ to 80 ℃.The heat treated temperature is high more, can obtain the effect of wanting more at short notice.40 ℃ or more low temperature, heat time heating time be when making coating liquid under 3 hours or the shorter condition, its whiteness is passed in time and the improved effect that descends is little.In addition, be higher than the stability that may influence composition under 90 ℃ the temperature, and may the printing sensitivity when making thermal recording medium bringing harmful effect.
(b) heating treatment method of composition (painted inhibitor) dispersion liquid is not particularly limited, and for example has: the dispersion composition that will comprise the painted inhibitor of (b) composition is packed in the container, on one side with stirrings such as paddle, the method for heating on one side; The method of in the process that the composition of the painted inhibitor that will comprise (b) composition is pulverized with pulverizers such as coating vibrating machine, ball mill, vibrator, grater, sand mill, Dyno mill, colloid mill, sand mills, heating; After normal temperature is pulverized, make temperature rising in the container, carry out stirring method etc. then.
(b) condition of the heat treated of the painted inhibitor dispersion liquid of composition was preferably carried out 3 hours at 40 ℃ to 90 ℃ proper temperature at least.Further preferably carried out at least 3 hours, more preferably carried out at least 4 hours at 55 ℃～75 ℃ at 50 ℃～80 ℃.The heat treated temperature is high more, can obtain the effect of wanting more at short notice.In the heat treated temperature is 40 ℃ or lower, heat treated time to be when making coating liquid under 3 hours or the shorter condition, and it is passed and the improved effect that descends is little in time from degree.In addition, be higher than the stability that may influence composition under 90 ℃ the temperature, and may the printing sensitivity when making thermal recording medium bringing harmful effect.
When to the dispersion liquid of the urea-carbamate compounds of (a) composition and (b) two compositions of the dispersion liquid of the painted inhibitor of composition carry out heat treated, can to (a) composition (urea-carbamate compounds) dispersion liquid and (b) composition (painted inhibitor) dispersion liquid carry out heat treated separately respectively, also can to (a) composition and (b) dispersion composition that is mixed with of the dispersion liquid of composition carry out heat treated (hereinafter referred to as heat treatment altogether), perhaps to by will (a) composition (urea-carbamate compounds) and (b) composition (painted inhibitor) mixing, the dispersion composition of pulverizing altogether and being prepared into carries out common heat treatment.By to make (a) composition (urea-carbamate compounds) and (b) dispersion composition of composition (painted inhibitor) coexistence carry out common heat treatment, the whiteness of using the coating liquid of this dispersion composition preparation is passed in time and the improved effect that descends and/or the moisture-proof background fog improved effect of recording materials further become big.
To making (a) composition (urea-carbamate compounds) and (b) condition the when dispersion composition of composition (painted inhibitor) coexistence carries out common heat treatment, preferably carried out at least 3 hours too at 40 ℃ to 90 ℃ proper temperature.Further preferably carried out at least 3 hours, more preferably carried out at least 4 hours at 55 ℃～75 ℃ at 50 ℃～80 ℃.The heat treated temperature is high more, can obtain the effect of wanting more at short notice.In the heat treated temperature is 40 ℃ or lower, heat treated time to be when making coating liquid under 3 hours or the shorter condition, and its whiteness is passed in time and the improved effect that descends is little.In addition, be higher than the stability that may influence composition under 90 ℃ the temperature, and may the printing sensitivity when making thermal recording medium bringing harmful effect.
In the painted inhibitor of the urea-carbamate compounds of (a) composition, (b) composition, the dispersion composition of the present invention that further comprises the acid developer of (c) composition, aforementioned (a) composition, (b) composition, (c) composition can be pulverized respectively separately and prepared dispersion liquid, carry out as required mixing each dispersion liquid after the heat treated, also can mix the dispersion composition that comprises at least a aforementioned (c) composition in addition to after with aforementioned (a) composition and (b) composition mixes, pulverizes the dispersion composition that forms altogether and carry out common heat treatment.
The concrete example of the dispersant during below to the acid developer of the painted inhibitor of urea-carbamate compounds of disperseing (a) composition, (b) composition, (c) composition is described.
The water soluble polymer concrete example that uses as dispersant if any: polyvinyl alcohol (below be designated as the PVA of PV (A), sulfonic acid modified, carboxyl acid modified PVA, polyacrylamide, PMAm, polyacrylic acid, polymethylacrylic acid, PEO, PPOX, polyvinylpyrrolidone or their synthetic high polymers such as copolymer; Methylcellulose, hydroxyethylcellulose, hydroxypropyl cellulose, HEMC, hydroxypropyl methylcellulose, the sanlose (cellulose family macromolecule of CM (C) etc. etc.
The concrete example of the surfactant that uses as dispersant, anion surfactant for example has: soap, alkyl sulfate salt, alkyl sulfo succinate, alkylphosphonic, polyxyethylated sulfuric acid, polyxyethylated pi-allyl sulfuric acid, aromatic sulfonic acid derivative (is repaiied the salt as alkyl benzene sulphonate, the salt of alkyl diphenyl base ether disulfonic acid, the salt of alkyl naphthalene sulfonic acid, the salt of naphthalene sulfonic acid-formaldehyde condensation product), poly carboxylic acid derivative's (for example various polymer or copolymer or their mixture that contains carboxylic monomer), polyxyethylated phosphate etc., non-ionic surface active agent for example has: polyoxyethylene alkyl ether, polyxyethylated allyl ether, oxygen ethylene oxy propylene-based block copolymer, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, the polyoxyethylene sorbitol fatty acid ester, fatty acid glyceride, polyoxyethylene fatty acid ester, polyoxyethylene alkyl amine, the alkyl alkanolamide, amphoteric surfactant for example has: alkyl betaine, amine oxide, the imidazoles betaine, other polyoxyethylene alkyl ether sulfuric acid triethanolamine (エ マ one Le 20T for example, flower king system), response type anion surfactant (ラ テ system Le S-180 for example, ラ テ system Le S-180A, flower king system), special high molecular surfactant (ホ モ ゲ ノ one Le L-95 for example, ホ モ ゲ ノ one Le L-100, flower king system).
Wherein, consider that from suppressing liquid photographic fog and background fog aspect the dispersant when dispersed urea-carbamate compounds and/or painted inhibitor preferably uses the PVA, hydroxypropyl methylcellulose (for example メ ト ロ one ズ (Metolose) 60SH03 (SHIN-ETSU HANTOTAI's chemistry system) etc.) of sulfonic acid modified, the salt of naphthalene sulfonic acid-formaldehyde condensation product (for example デ モ one Le T (flower king system) etc.), poly carboxylic acid derivative (for example デ モ one Le EP (flower king system) etc.).
These dispersants can use separately also and can two or more use simultaneously, also can use dispersant water soluble polymer commonly used, anion surfactant, non-ionic surface active agent, cationic surfactant, the amphoteric surfactant in addition that is recorded in concrete example as required simultaneously, for example alkylamine salt, quaternary ammonium salt, amine oxide etc.
On arbitrary support, form color layer by the coating liquid that will contain composition of the present invention with methods such as coatings and can make recording materials, when making recording materials, can use known any additive as required.Below described.
As the leuco dye of an example of the colourless or light dyestuff former that is used for color layer, be the known compound that is used for pressure sensitive recording material and thermal recording medium, do not limit for example following material especially.
(1) triarylmethane compounds
3, two (to the dimethylamino phenyl)-6-dimethylamino phthalides (crystal violet lactone) of 3-, 3, two (to the dimethylamino phenyl) phthalides of 3-, 3-(to dimethylamino phenyl)-3-(1,2-dimethyl indole-3-yl) phthalide, 3-(to dimethylamino phenyl)-3-(2 methyl indole-3-yl) phthalide, 3-(to dimethylamino phenyl)-3-(2-phenylindone-3-yl) phthalide, 3,3-two (1,2-dimethyl indole-3-yl)-5-dimethylamino phthalide, 3,3-two (1,2-dimethyl indole-3-yl)-6-dimethylamino phthalide, 3, two (9-ethyl carbazole-3-the yl)-5-dimethylamino phthalides of 3-, 3, two (2-phenylindone-3-the yl)-5-dimethylamino phthalides of 3-, 3-is right-dimethylamino phenyl-3-(1-methylpyrrole-2-yl)-6-dimethylamino phthalide etc.
(2) diphenyl-methane compounds
4,4-is two-dimethylamino phenyl benzhydryl benzylic ether, the colourless auramine of N-halogenophenyl, N-2,4, the colourless auramine of 5-trichlorophenyl etc.
(3) xanthene compounds
Rhodamine B anilino-lactams, rhodamine B-right-chloroanilino lactams, 3-lignocaine-7-dibenzyl amino fluorane, the amino fluorane of 3-lignocaine-7-octyl group, 3-lignocaine-7-phenyl fluorane, 3-lignocaine-7-chlorine fluorane, 3-lignocaine-6-chloro-7-methyl fluoran, 3-lignocaine-7-(3,4-dichloro-benzenes amido) fluorane, 3-lignocaine-7-(2-chloroanilino) fluorane, 3-lignocaine-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-tolyl) amino-6-methyl-7-anilino fluorane, 3-piperidino-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-tolyl) amino-6-methyl-7-phenethyl fluorane, 3-lignocaine-7-(4-nitrobenzene amido) fluorane, 3-dibutylamino-6-methyl-7-anilino fluorane, 3-(N-methyl-N-propyl group) amino-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isopentyl) amino-6-methyl-7-anilino fluorane, 3-(N-methyl-N-cyclohexyl) amino-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-tetrahydrofuran base) amino-6-methyl-7-anilino fluorane etc.
(4) thiazides compounds
Benzoyl leucomethylene blue, p-nitrophenyl formyl leukomethylene etc.
(5) volution compound
3-methylspiro dinaphthopyran, 3-ethyl spiral shell dinaphthopyran, 3,3-dichloro spiral shell dinaphthopyran, 3-benzyl spiral shell dinaphthopyran, 3-methyl naphtho--(3-methoxyl group benzo) spiro-pyrans, 3-propyl group spiral shell dibenzopyrans etc.
In addition, 3, two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-dimethylamino phthalide), 3-lignocaine-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dimethylamino phthalide), 3, two (lignocaine) fluorenes of 6--9-spiral shell-3 '-(6 '-dimethylamino phthalide), 3-dibutylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dimethylamino phthalide), 3-dibutylamino-6-lignocaine fluorenes-9-spiral shell-3 '-(6 '-dimethylamino phthalide), 3, two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-lignocaine phthalide), 3-lignocaine-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-lignocaine phthalide), 3-dibutylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-lignocaine phthalide), 3, two (lignocaine) fluorenes of 6--9-spiral shell-3 '-(6 '-lignocaine phthalide), 3, two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-dibutylamino phthalide), 3-dibutylamino-6-lignocaine fluorenes-9-spiral shell-3 '-(6 '-lignocaine phthalide), 3-lignocaine-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dibutylamino phthalide), 3, two [2-(4-dimethylamino phenyl)-2-(4-methoxyphenyl) vinyl]-4 of 3-, 5,6,7-Rabcide etc. have the compound of absorption region etc. at near-infrared.
With respect to colourless or light dyestuff former 100 mass parts, preferably use urea-carbamate compounds 5～500 mass parts, more preferably 20～300 mass parts.Urea-carbamate compounds is 5 mass parts or more, makes the dyestuff former colour developing fully, and colour developing concentration is also high.In addition, urea-carbamate compounds is 500 mass parts or still less, and superfluous urea-carbamate compounds is difficult to residual, also preferred economically.
The dispersion liquid of colourless or light dyestuff former, all it doesn't matter to carry out or do not carry out heat treated, but by carrying out heat treated, the whiteness that can improve coating liquid reduces the improved effect of the moisture-proof background fog of improved effect and/or recording materials.
Contain the hot melt material in the composition in order to improve the developing sensitivity of recording materials, can to make.The hot melt material preferably has the material of 60 ℃～180 ℃ fusing point, especially preferably has the material of 80 ℃～140 ℃ fusing point.For example have: hard esteramides, palmitamide, the hard esteramides of N-methylol, the betanaphthyl benzylic ether, the hard ester group urea of N-, N, the hard ester group urea of N '-two, β-naphthoate, 1-hydroxyl-2-naphthoate, betanaphthol (to methylbenzyl) ether, 1, the 4-dimethoxy-naphthalene, 1-methoxyl group-4-benzyloxy naphthalene, the hard ester uride of N-, to benzylbiphenyl, 1, two (methylphenoxy) ethane of 2-, 1-phenoxy group-2-(4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate (DMT), meta-terphenyl, dibenzyl oxalate, oxalic acid (p-chlorobenzyl) ester, 4-Para Hydroxy Benzoic Acid methyl esters, 4-Para Hydroxy Benzoic Acid benzyl ester, 4-Para Hydroxy Benzoic Acid (4 '-benzyl chloride ester), 1, two (4 '-Para Hydroxy Benzoic Acid) ethyl esters of 2-, 1, two (4 '-Para Hydroxy Benzoic Acid) pentyl esters of 5-, 1, two (4 '-Para Hydroxy Benzoic Acid) own esters of 6-etc.And, also can use 4,4 '-dimethoxy-benzophenone, 4,4 ' dichloro benzophenone, 4,4 '-difluoro benzophenone, diphenyl sulphone (DPS), 4,4 '-dichloro diphenyl sulfone, 4,4 '-difluorodiphenyl sulfone, 4,4 '-dichloro diphenyl disulphide, diphenylamines, 2-methyl-4-methoxy diphenylamine, N, N '-diphenyl-p-phenylenediamine (PPD), 1-(N-phenyl amino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione etc.
Aforementioned hot fusibleness material can use separately, also can two or more mix use, in order to obtain sufficient hot responsiveness, with respect to colourless or light dyestuff former, preferably uses 10～500 quality %, and, more preferably use 20～300 quality %.
In the composition of the present invention, by further interpolation isocyanate compound, keeping quality improves.The isocyanate compound that can add in the composition of the present invention, be to be the colourless or light aromatic isocyanate compound or the heterocycle isocyanate compound of solid at normal temperatures, can add at least a of the isocyanate compound put down in writing among the international publication number WO00/14058 for example.These isocyanates, as required can use and the form of the so-called blocked isocyanate of the additive compound of phenols, lactams, oximes etc., the dimer of vulcabond is 1-methylbenzene-2 for example, the dimer of 4-vulcabond and also can use as the form of trimerical isocyanuric acid ester, in addition, also can use polyisocyanates with additions such as various polyalcohols.In addition, also can be 2, water adduction isocyanates such as 4-toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, phenol adduction isocyanates, amine adduction isocyanates etc., special isocyanate compound and isocyanates of being willing to that flat 8-225445 specification, the flat 8-250623 specification of special hope are put down in writing add fit compound.
With respect to colourless or light dyestuff former, preferably use isocyanate compound 5～500 quality %, more preferably 20～200 quality %.Isocyanate compound is 5 quality % or more, and the raising effect of storage life is abundant, and colour developing concentration is also high.In addition, isocyanate compound is 500 quality % or lower, and superfluous isocyanate compound is difficult to residual, also preferred economically.
In addition, by add imino-compound in composition of the present invention, its keeping quality further improves.
The imino-compound that can add in the composition of the present invention is meant the colourless or light compound of the normal temperature solid with at least one imino group, also can use the imino-compound of two or more as required simultaneously.As its concrete example, can enumerate the material of putting down in writing among the international publication number WO00/14058 for example.
In these materials, preferred especially imino group isoindoline derivative, and, preferred 1,3-diimino-4,5,6,7-tetrachloro isoindoline, 3-imino group-4,5,6,7-tetrachloro 1-isoindolinone, 1,3-diimino-4,5,6,7-tetrabromo isoindoline.
With respect to colourless or light dyestuff former, preferably use imino-compound 5～500 quality %, more preferably 20～200 quality %.Imino-compound is 5 quality % or more, can bring into play conservatory raising effect.In addition, imino-compound is 500 quality % or lower, and superfluous imino-compound is difficult to residual, also preferred economically.
By further add amino-compound in composition of the present invention, the storage life of background and printing improves.The amino-compound that can add is the colourless or light material with at least one primary amino radical or secondary amino group or uncle's amino, for example anil of putting down in writing among the international publication number WO00/14058, heterocycle compound, hindered amine compound etc.
Amino-compound can use separately, also can two or more mix use, and in order to improve the printing storage life in the plasticizer resistance properties, with respect to colourless or light dyestuff former, amino-compound is preferably 1～500 quality %.The content of amino-compound is 1 quality % or higher with respect to urea-carbamate compounds, can improve the printing keeping quality.In addition,, just can fully improve performance as long as use 500 quality % or lower, also favourable on the cost.
And; in order to improve background fog and hot responsiveness etc.; also can add the hard ester group-N ' of N--(2-hydroxy phenyl) urea; hard ester group-the N ' of N--(3-hydroxy phenyl) urea; hard ester group-the N ' of N--(4-hydroxy phenyl) urea; right-hard ester acyl aminophenols; adjacent-hard ester acyl aminophenols; right-the lauroyl amino-phenol; right-the bytyry amino-phenol; between-acetyl-amino phenol; o-acetyl-base amino-phenol; right-acetyl-amino phenol; neighbour-Ding amino carbonyl phenol; adjacent-hard ester group amino carbonyl phenol; right-hard ester group amino carbonyl phenol; 1; 1; 3-three (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) butane; 1; 1; 3-three (3-tertiary butyl-4-hydroxy-6-ethylphenyl) butane; 1; 1; 3-three (3; the 5-di-tert-butyl-hydroxy phenyl) butane; 1; 1; 3-three (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) propane; 1; 2; 3-three (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) butane; 1; 1; 3-three (3-phenyl-4-hydroxy phenyl) butane; 1; 1; 3-three (3-cyclohexyl-4-hydroxy-5-methyl base phenyl) butane; 1; 1; 3-three (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) butane; 1; 1; 3-three (3-phenyl-4-hydroxy phenyl) propane; 1; 1; 3; 3-four (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) propane; 1; two (3-tertiary butyl-4-hydroxy-6-aminomethyl phenyl) butane of 1-; 1, phenolic compounds such as two (3-cyclohexyl-4-hydroxyl-6-aminomethyl phenyl) butane of 1-.
Composition of the present invention can be used as various recording materials such as thermal recording medium, pressure sensitive recording material and uses, and is particularly suitable as thermal recording medium.
When recording materials are thermal recording medium, must on support, be provided for heating the heat sensitive recording layer of colour developing.Specifically, to contain urea-carbamate compounds, (b) composition of above-mentioned (a) composition painted inhibitor, (c) composition acid developer and for example colourless the or light dyestuff former, hot melt material etc. of leuco dye dispersion composite and form other necessary composition of heat sensitive recording layer and be prepared, mix as dispersion liquid, preparation coating liquid, further should apply liquid and be coated on the support, form heat sensitive recording layer.Each dispersion liquid obtains by the following method: use dispersion machines such as sand mill, dispersants such as one or more that will select from all cpds that exemplifies before and water soluble polymer, surfactant are scattered in the water together, and it is broken to carry out micro mist.At this, (a) composition (urea-carbamate compounds) and/or (b) composition (painted inhibitor) and/or (c) composition (acid developer) must use as dispersion composition specific in the present application.The particle diameter of the dispersate in the dispersion liquid is not particularly limited, but as required, the particle diameter of each dispersion is preferably 0.1～10 μ m.More preferably about 0.1～2 μ m.
Other composition in the heat sensitive recording layer exemplifies as follows.
As pigment, for example can contain: diatomite, talcum, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silica, aluminium hydroxide, urea-formaldehyde resins etc.A part of composition of pigment and the application's painted inhibitor repeats, and with respect to developer 100 mass parts, the use amount of pigment is 50～400 mass parts usually, does not manifest the function that suppresses painted fully.But beyond thought is that the application's painted inhibitor finds to have painted inhibition effect by urea-carbamate compounds and/or painted inhibitor are carried out heat treated.In addition, with respect to developer 100 mass parts, painted inhibitor so long as 1 to～less than 50 parts, will manifest abundant effect.
In addition, wear away, prevent adhesion etc., it is contained: senior fatty acid metal salts such as zinc stearate, calcium stearate in order to prevent thermal head (head); Wax classes such as paraffin, oxidized paraffin wax, polyethylene, oxidic polyethylene, hard esteramides, castor wax, in addition, also can make it contain ultra-violet absorbers such as dispersant, benzophenone, benzotriazole, image preservative agent, fade inhibitor and surfactant, fluorescent dyes etc. such as dioctyl sodium sulphosuccinate as required.
The binding agent that can be used for heat sensitive recording layer formation for example has: starch based, hydroxyethylcellulose, methylcellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinylalcohol, Sodium Polyacrylate, acrylamide/acrylate copolymer, acrylamide/acrylate/metering system acid ter-polymer, the alkali salt of phenylethylene/maleic anhydride copolymer, the water-soluble binders such as alkali salt of ethene/copolymer-maleic anhydride; The water-fast binding agents of latex class such as styrene/butadiene copolymers, acrylonitrile/butadiene copolymer, methyl acrylate/butadiene copolymer etc.
The support of heat sensitive recording layer mainly uses paper, but also can use various fabrics beyond the paper, nonwoven, synthetic resin film, laminated paper, synthetic paper, metal forming as required arbitrarily or with these composite sheets that combines.Heat sensitive recording layer can be made of individual layer, also can be made of multilayer.For example can make each layer contain the multi-ply construction of each color composition.In addition, on this heat sensitive recording layer, the protective layer that is made of one or more layers can be set, between support and heat sensitive recording layer, the intermediate layer that is made of one or more layers can be set.This heat sensitive recording layer can by each color composition or other composition are carried out mixing such as broken various aqueous liquid dispersions that obtain of micro mist and binding agent, coating on support, dry obtaining.In the dried state of coating liquid, coating amount is preferably 1～15g/m 2
When recording materials are the pressure sensitive recording material, can adopt for example No. 2505470 communique of United States Patent (USP), No. 2712507 communiques of United States Patent (USP), No. 2730456 communiques of United States Patent (USP), No. 2730457 communiques of United States Patent (USP), No. 3418250 disclosed modes such as communique of United States Patent (USP).That is, following variety of way can be arranged: separately or mix with dyestuff former, be dissolved in by alkylated naphthalene, alkylated biphenyls, the alkylation diphenyl-methane, the alkylation diarylethane, artificial oils such as chlorinated paraffin wax, vegetable oil, animal oil, in the medium that the mineral wet goods is independent or mixture constitutes, it is scattered in the binding agent, perhaps be coated on the dispersion liquid that contains in the microcapsules and binding agent etc. on the support together, obtain upper paper thus, make it and applied between the applicator surface of lower floor's paper of coating liquid of the dispersion composition of the present invention that contains the urea-carbamate compounds that comprises (a) composition (and amino-compound or developer etc.) and overlap the formation pressure sensitive recording paper; Perhaps, the coating liquid that further contains the dispersion composition of the present invention of the urea-carbamate compounds that comprises (a) composition in the single face coating, in another side coating dyestuff former forms, use paper, it is clipped in the pressure sensitive recording paper that forms between above-mentioned upper paper and the lower floor's paper; Perhaps, on the same one side of support, the coating liquid that the dispersion composition that coating will comprise the dispersion composition of the present invention of above-mentioned (a) composition (urea-carbamate compounds) and (and amino-compound or developer) and the dispersion composition that comprises above-mentioned dyestuff former mix, the automatic type that perhaps on multilayer, applies (self-type), maybe will comprise dyestuff former, (a) any microencapsulation of the dispersion composition of the present invention of composition (urea-carbamate compounds) (and amino-compound or developer etc.), the automatic type that the mixing coating forms etc.
When being the use of pressure sensitive recording material,, can obtain the colour developing pressure sensitive recording material of the distinctness of image color raising by adding the acid developer of (c) composition with dispersion composition of the present invention.(c) composition (acid developer) also can be the material in addition that particular instantiation is crossed, specifically can use electronics to accept material, for example have: inorganic compounds such as Emathlite, atlapulgite, attapulgite, bentonite, zeolite, colloidal silica, magnesium silicate, talcum, alumina silicate; Or phenol, cresols, butylphenol, octyl phenol, phenylphenol, chlorophenol, salicylic acid etc.; Or by its aldehyde condensation phenolic resins of deriving and their metal salt compound, 3-isopropyl salicylic acid, 3-phenylo salicylic acid, 3-cyclohexyl salicylic acid, 3,5-di-tert-butyl salicylic acid, 3,5-two (α-Jia Jibianji) salicylic acid, 3,5-two uncle's octyl group salicylic acids, 3-methyl-5-benzyl salicylic acid, 3,5-two (α, α-Er Jiajibianji) salicyclic acid derivatives such as salicylic acid, 3-phenyl-5-(α, α-Er Jiajibianji) salicylic acid and their metal salt compound etc.Acid developer when using as the pressure sensitive recording material, a part of inorganic compound and the application's painted inhibitor repeats, but these compounds use as the developer that makes the dyestuff former colour developing at present, do not manifest the function that suppresses painted fully.But beyond thought is that the application's painted inhibitor finds to have and make the antipodal painted inhibit feature of coloring function of dyestuff former colour developing by urea-carbamate compounds and/or painted inhibitor are carried out heat treated.
In the recording materials of the present invention, its recording layer can further contain the ultra-violet absorber, image preservative agent, fade inhibitor, light stabilizer of hindered phenol compound representative etc.For example have: 1,1,3-three (3 '-cyclohexyl-4 '-hydroxy phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, three (2,6-dimethyl-4-the tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester, 4,4 '-sulphur two (3-methyl-6 tert-butyl phenol), 4,4 '-butylidene two (3-methyl-6-tert butyl phenyl), 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 2,2 '-dihydroxy-4,4 '-dimethoxy-benzophenone, OPS p octylphenyl salicylate, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA, 2-cyano group-3,3 '-diphenyl-ethyl acrylate, 1,2,3,4-BTCA four (2,2,6,6-tetramethyl-4-piperidyl) ester, 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) sodium phosphite etc.
Embodiment
Below, by embodiment and comparative example the present invention is carried out more specific description.
The evaluation of each rerum natura is carried out by the following method.Need to prove that in the explanation, part and % are not specifically noted and represent mass parts and quality % respectively.
＜printing sensitivity 〉
With big storehouse motor seal carving brushes testing machine, thermal head uses capital セ ラ system KJT-256-8MGF1, is determined at Macbeth (Macbeth) optical concentration meter RD918 that to apply voltage be that 24V, pulse width are the colour developing concentration under the 1.5msec condition.
＜moisture-proof background fog 〉
Make electrothermal sensitive recording paper, this electrothermal sensitive recording paper is carried out humidity test (placing 24 hours) under 40 ℃, the environment of relative humidity 90%.Measure the whiteness (W) of the not Printing Department (background) of humidity test front and back, estimate the improved effect of moisture-proof background fog according to its variable quantity (Δ W).(measure by Suga testing machine (Suga Test Instruments Co., Ltd) system) with touch panel formula color computer-SM-T for whiteness.With the whiteness variable quantity little be evaluated as the effect height.Evaluation criterion is recorded in the footnote of each table.
The mensuration of whiteness: instrument: touch panel formula SM color computer-SM-T (Suga testing machine)
Light source: D65 light, 10 ° of visuals field, 12V 50W Halogen lamp LED
Condition determination: measure reverberation (light is accepted in 8 ° of diffusions, removes normal reflection light)
D is a standard with JIS Z8722 condition
Measure the hole: Ф 30mm
The whiteness of＜dispersion composition 〉
Preparation contains the dispersion liquid of colourless or light dyestuff former 5%, developer 10%, painted inhibitor 1%, as painted evaluation sample.Use this sample,, under 40 ℃ of conditions, place 3h, carry out accelerated test in order to quicken coloring phenomenon.Measure the whiteness (W) of the sample of accelerated test front and back, estimate the performance of painted inhibitor according to its variable quantity (Δ W).(measure by Suga testing machine (Suga Test Instruments Co., Ltd) system) with touch panel formula color computer-SM-T for whiteness.With the whiteness variable quantity little be evaluated as the effect height.Evaluation criterion is recorded in the footnote of each table.
The mensuration of＜size distribution 〉
Particle diameter (the D of dispersion composition 50) measure with SALD-7000LASER DIFFRACTIONPARTICLE SIZE ANALYZER (Shimadzu Seisakusho Ltd.'s system).
Synthesizing of＜urea-carbamate compounds 〉
2, add ethyl acetate 112.4g among 4-toluene di-isocyanate(TDI) 105.6g, the phenol 68.4g as solvent.Therein with 4,4 '-DADPS divides 8 each 9.41g to add, Yi Bian stirred 1 hour on one side.The reactant liquor paste-like that is white in color.Then, adding 361.8g ethyl acetate in reactant mixture dilutes.The reactant mixture that will dilute on one side is warming up to 60 ℃ with the speed of 10 ℃/h from 30 ℃, one side with the ethyl acetate solution 18.1g of the triethylamine of interpolation 0.375% in 30 minutes.After arriving 60 ℃, further continue reaction 15 hours at 60 ℃.This reactant mixture is cooled to 30 ℃ from 60 ℃, adds 2,4-toluene di-isocyanate(TDI) 15.8g stirred 1 hour at 30 ℃, finished reaction.Then, by under reduced pressure, removing ethyl acetate, under nitrogen atmosphere, 65 ℃, about 130torr carry out 8 hours drying under reduced pressure, obtain 265g white crystals urea-carbamate compounds (below be designated as UU).
＜dispersion liquid preparation example 1: dye dispersion liquid preparation 〉
With the 3-dibutylamino-6-methyl-7-anilino fluorane of dyestuff former (below be designated as ODB2) 52.5g, 5.38% go one セ ラ Application (Gohseran) L3266 (PVA of sulfonic acid modified, Japan's synthetic chemistry system) aqueous solution 97.5g and the 150ml bead of measuring (Ф 0.710mm～0.990mm) with graduated cylinder, sand mill (ア イ メ Star Network ス (AIMEX Co. packs into, Ltd) in 400ml container society's system), at revolution is under the condition of 2000rpm, carries out grinding dispersion 3 hours.After filtering out bead, the dispersion liquid that obtains is packed in the 200ml flask, use Three-One Motor under 250rpm, to stir 24 hours at 40 ℃, ODB2 is carried out heat treated by make in the flask temperature maintenance with thermostat.(the nonvolatile component containing ratio is 38.5% to the 35%ODB2 dispersion liquid that obtains like this; Describe in detail: the ODB2 containing ratio is 35%, dispersant L3266 containing ratio is 3.5%) average grain diameter be 0.49 μ m.
＜dispersion liquid preparation example 2:UU dispersion liquid preparation 〉
(in the 400ml container of ア イ メ Star Network ス (AIMEX Co., Ltd) society's system), inject 20% go, one セ ラ Application L3266 (PVA of sulfonic acid modified, Japanese synthetic chemistry system) aqueous solution 30g, add distilled water 60g and dilute at sand mill.The 150ml bead of packing developer UU60g therein into and measuring with graduated cylinder (Ф 0.710mm～0.990mm), be under the condition of 2000rpm at revolution, carried out grinding dispersion 3 hours.Filter out bead, (the nonvolatile component containing ratio is 44% to obtain the 40%UU dispersion liquid; Describe the UU containing ratio in detail and be 40%, dispersant L3266 containing ratio is 4%).The measurement result of the average grain diameter of this 40%UU dispersion liquid is as shown in table 1.
Developer dispersion preparation beyond＜dispersion liquid preparation example 3～8:UU 〉
(in the 400ml container of ア イ メ Star Network ス (AIMEX Co., Ltd) society's system), inject 20% go, one セ ラ Application L3266 (PVA of sulfonic acid modified, Japanese synthetic chemistry system) aqueous solution 30g, add distilled water 60g and dilute at sand mill.Use D-8 (dispersion liquid preparation example 3), BPA (dispersion liquid preparation example 4), BPS (dispersion liquid preparation example 5), 2,4 '-BPS (dispersion liquid preparation example 6), TGSA (dispersion liquid preparation example 7), POB (dispersion liquid preparation example 8) substitute developer UU60g, with the 150ml bead of measuring (Ф 0.710mm～0.990mm) pack into together wherein with graduated cylinder, at revolution is under the condition of 2000rpm, carries out grinding dispersion 3 hours.Filter out bead, (the nonvolatile component containing ratio is 44% to 40% developer dispersion that is recovered to; Describe the UU containing ratio in detail and be 40%, dispersant L3266 containing ratio is 4%) the measurement result of average grain diameter as shown in table 1.
＜dispersion liquid preparation example 9-1,9-2: the preparation of magnesium silicate dispersion liquid 〉
With magnesium silicate (ト ミ AD-600, rich field pharmacy system) 2g, 2.5% go one セ ラ Application (Gohseran) L3266 (PVA of sulfonic acid modified, Japan's synthetic chemistry system) aqueous solution 8g and alumina bead (Ф 3mm) 60g are measured in the 50ml plastic containers, pulverized 1 hour with coating vibrating machine (shallow field ironworker's system), (average grain diameter 1.5 μ m, nonvolatile component containing ratio are 22% to obtain the 20% magnesium silicate dispersion liquid of dispersion liquid preparation example 9-1; Describe the magnesium silicate containing ratio in detail and be 20%, dispersant L3266 containing ratio is 2%).
In addition, by with the coating vibrating machine it being pulverized 12 hours, (average grain diameter 0.4 μ m, nonvolatile component containing ratio are 22% to obtain the 20% magnesium silicate dispersion liquid of dispersion liquid preparation example 9-2; Describe the magnesium silicate containing ratio in detail and be 20%, dispersant L3266 containing ratio is 2%).
＜dispersion liquid preparation example 10-1,10-2:UU and magnesium silicate heat treatment dispersion liquid preparation altogether 〉
Prepare the 1000ml flask, the 20% magnesium silicate dispersion liquid 120g (UU solid constituent amount/magnesium silicate solid constituent amount=100/10) of mixed dispersion liquid preparation example 9-1 preparation in the 40%UU dispersion liquid 600g of dispersion liquid preparation example 2 preparations.Make in the flask temperature maintenance at 60 ℃ with thermostat, under 500rpm, stirred 48 hours, this mixed dispersion liquid is carried out common heat treatment, obtain UU and the common heat treatment dispersion liquid of magnesium silicate of dispersion liquid preparation example 10-1 with Three-One Motor.
In addition, by being replaced as the 20% magnesium silicate dispersion liquid 120g (UU solid constituent amount/magnesium silicate solid constituent amount=100/10) of dispersion liquid preparation example 9-2 preparation, carry out heat treatment altogether in 24 hours, the UU and the magnesium silicate that obtain dispersion liquid preparation example 10-2 are total to the heat treatment dispersion liquid.
＜dispersion liquid preparation example 11-1,11-2: the preparation of sensitizer dispersion liquid 〉
(in the 400ml container of ア イ メ Star Network ス (AIMEX Co., Ltd) society's system), inject 20% go, one セ ラ Application L3266 (PVA of sulfonic acid modified, Japanese synthetic chemistry system) aqueous solution 30g, add distilled water 60g and dilute at sand mill.The 150ml bead of packing sensitizer diphenyl sulphone (DPS) (below be designated as DP) 60g therein into and measuring with graduated cylinder (Ф 0.710mm～0.990mm), be under the condition of 2000rpm at revolution, carried out grinding dispersion 3 hours.Filter out bead, (average grain diameter 0.60 μ m, nonvolatile component containing ratio are 44% to obtain the 40%DP dispersion liquid of dispersion liquid preparation example 11-1; Describe the DP containing ratio in detail and be 40%, dispersant L3266 containing ratio is 4%).
In addition, pulverize equally by sensitizer DP being replaced as sensitizer benzyloxy naphthalene (below be designated as BON), (average grain diameter 0.59 μ m, nonvolatile component containing ratio are 44% to obtain the 40%BON dispersion liquid of dispersion liquid preparation example 11-2; Describe the BON containing ratio in detail and be 40%, dispersant L3266 containing ratio is 4%).
＜dispersion liquid preparation example 12: calcium carbonate disperses the liquid preparation 〉
Calcium carbonate 10g (カ Le ラ イ ト KT, Bai Shi カ Le シ ウ system industry system) and water 30g are mixed, carry out dispersed with stirring, obtain 25% calcium carbonate and disperse liquid with magnetic stirrer.
＜dispersion liquid preparation example 13:UU and magnesium silicate are pulverized common heat treatment dispersion liquid preparation altogether 〉
(in the 400ml container of ア イ メ Star Network ス (AIMEX Co., Ltd) society's system), inject 20% go, one セ ラ Application L3266 (PVA of sulfonic acid modified, Japanese synthetic chemistry system) aqueous solution 30g, add distilled water 67.5g and dilute at sand mill.The 150ml bead of packing developer UU50g, magnesium silicate (ト ミ AD-600, rich field pharmacy system) 5g therein into and measuring with graduated cylinder (Ф 0.710mm～0.990mm), be under the condition of 2000rpm at revolution, carried out grinding dispersion 3 hours.Filter out bead, (the nonvolatile component containing ratio is 40.3% to obtain the 33.3%UU dispersion liquid; Describe the UU containing ratio in detail and be 33.3%, the magnesium silicate containing ratio is 3.3%, dispersant L3266 containing ratio is 3.7%).The measurement result of the average grain diameter of this UU dispersion liquid is as shown in table 1.
Prepare the 200ml flask, make with thermostat that temperature maintenance stirred 48 hours with Three-One Motor at 60 ℃ in the flask under 300rpm, common grinding dispersion liquid 120g carries out common heat treatment to this UU-magnesium silicate.
[table 1]
Developer Average grain diameter [μ m]
Dispersion liquid preparation example 2 UU 0.34
Dispersion liquid preparation example 3 D-8 0.43
Dispersion liquid preparation example 4 BPA 0.84
Dispersion liquid preparation example 5 BPS 0.43
Dispersion liquid preparation example 6 2，4′-BPS 0.70
Dispersion liquid preparation example 7 TGSA 0.41
Dispersion liquid preparation example 8 POB 0.42
Dispersion liquid preparation example 13 The UU-magnesium silicate is pulverized altogether 0.42
[embodiment 1]
35% dispersion liquid of dyestuff former dyestuff 3-dibutylamino-6-methyl-7-anilino fluorane (below be designated as ODB2) is with the method preparation of dispersion liquid preparation example 1.
40%UU heat treatment dispersion liquid obtains by the following method: after the method preparation with dispersion liquid preparation example 2, in the 200ml flask of packing into, make with thermostat that temperature maintenance stirred 24 hours with Three-One Motor at 60 ℃ in the flask under 250rpm.
The dispersion liquid of sensitizer diphenyl sulphone (DPS) (below be designated as DP) by disperseing DP with the method for dispersion liquid preparation example 11-1, obtains the 40%DP dispersion liquid.
25% calcium carbonate disperses liquid to utilize the method preparation of dispersion liquid preparation example 12.
The evaluation of the moisture-proof background fog of heat-sensitive paper is carried out with following program.
It (all is the stem body standard that these dispersion liquids are 30 parts by UU.As follows), ODB2 is that 15 parts, DP are that 30 parts, calcium carbonate are 20 parts, to also have zinc stearate (Zhong jing grease system Ha イ De リ Application (Hidorin) Z-7-30) be 10 parts, also have polyvinyl alcohol (Network ラ レ system Port バ one Le PVA110 to be prepared into the use of 15% aqueous solution.) be 10 parts ratio cooperation, mix, obtain applying liquid.
Should apply liquid with scraping strip coating machine is coated in and has 50g/m 2On the body paper of basic weight, handle with supercalender dry back, obtains electrothermal sensitive recording paper.At this moment coating amount is scaled 0.40g/m with ODB2 2
The heat-sensitive paper that is made into was like this placed 24 hours under 40 ℃, relative humidity 90% environment,, estimated the moisture-proof background fog of heat-sensitive paper by measuring the background whiteness before and after it.The result is as shown in table 2.
In addition, the whiteness of dispersion composition is estimated by following program.
The ODB that the UU that crosses by heat treated is 10%, heat treated is crossed 25% is prepared, and obtains estimating sample.Should estimate sample and carry out painted accelerated test (under 40 ℃ of conditions, placing 3h), measure the whiteness of its front and back.The result is as shown in table 2.Evaluation result is that the moisture-proof background fog is that △, dispersion composition whiteness are △, confirms to have the effect of improvement.
[embodiment 2]
In embodiment 1, when utilizing dispersion liquid preparation example 2 to carry out the grinding dispersion of UU, メ ト ロ one ズ (Metolose) of use 20% is 60SH03 (hydroxypropyl methylcellulose (Metolose), SHIN-ETSU HANTOTAI's chemical industry system) aqueous solution 12g and 20% デ モ one Le (Demol) T (beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt, flower king system) aqueous solution 12g replaces 20% go one セ ラ Application (Gohseran) L3266 aqueous solution 30g, adding water is 66g, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.Evaluation result is that the moisture-proof background fog is that △, dispersion composition whiteness are △, confirms to have the effect of improvement.
[embodiment 3]
The magnesium silicate dispersion liquid that adds in UU30 part in embodiment 1 as the dispersion liquid preparation example 9-2 preparation of painted inhibitor is added 3 parts by magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.Need to prove that 20% magnesium silicate dispersion liquid of painted inhibitor adds after UU dispersion liquid heat treated.Evaluation result is that the moisture-proof background fog is zero, the dispersion composition whiteness is zero, has confirmed by adding the further effect of improving that the magnesium silicate dispersion liquid brings.
[embodiment 4]
In embodiment 3, use 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-t-butyl) sodium phosphate (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) F-85) replaces the magnesium silicate of dispersion liquid preparation example 9-2 use, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 5]
In embodiment 3, the magnesium silicate that uses titanium oxide (titanium industry system KA15) to replace dispersion liquid preparation example 9-2 to use, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 6]
In embodiment 3, the magnesium silicate that uses calcium carbonate (Bai Shi カ Le シ ウ system industry system カ Le ラ イ ト KT) to replace dispersion liquid preparation example 9-2 to use, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 7]
In embodiment 3, the magnesium silicate that uses calcium sulfate (with the pure pharmaceutical worker's industry of light reagent) to replace dispersion liquid preparation example 9-2 to use, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 8]
In embodiment 3, do not carry out the heat treated of UU dispersion liquid, and the magnesium silicate dispersion liquid is carried out heat treated, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
Need to prove that the heat treated of the magnesium silicate dispersion liquid of painted inhibitor is carried out in order to following method.
The dispersion liquid that dispersion liquid preparation example 9-2 is obtained places the 50ml plastic containers, makes in the flask temperature maintenance at 60 ℃ with thermostat, stirs 24 hours with magnetic stirrer, and painted inhibitor dispersion liquid is carried out heat treated.
[embodiment 9]
In embodiment 8, use 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-t-butyl) sodium phosphate (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) F-85) replaces the magnesium silicate of dispersion liquid preparation example 9-2 use, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 10]
In embodiment 8, the magnesium silicate that uses titanium oxide (titanium industry system KA15) to replace dispersion liquid preparation example 9-2 to use, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 11]
In embodiment 8, the magnesium silicate that uses calcium carbonate (Bai Shi カ Le シ ウ system industry system カ Le ラ イ ト KT) to replace dispersion liquid preparation example 9-2 to use, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 12]
In embodiment 8, the magnesium silicate that uses calcium sulfate (with the pure pharmaceutical worker's industry of light reagent) to replace dispersion liquid preparation example 9-2 to use, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 13]
In embodiment 3, use the UU and the magnesium silicate mixed dispersion liquid of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.Evaluation result is that the moisture-proof background fog is zero, the dispersion composition whiteness is zero, has confirmed further to improve effect than the situation of having added the magnesium silicate dispersion liquid among the embodiment 3.
[embodiment 14]
In embodiment 13, use magnesia (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 15]
In embodiment 13, use magnesium carbonate (refreshing island chemical industry system Venus) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 16]
In embodiment 13, use magnesium phosphate (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 17]
In embodiment 13, use magnesium hydroxide (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 18]
In embodiment 13, use aluminium oxide (STREM CHEMICALS reagent) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 19]
In embodiment 13, use calcium silicates (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 20]
In embodiment 13, use calcium carbonate (Bai Shi カ Le シ ウ system industry system カ Le ラ イ ト KT) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 21]
In embodiment 13, use calcium sulfate (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 22]
In embodiment 13, use titanium oxide (titanium industry system KA15) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 23]
In embodiment 13, when the grinding dispersion of the UU of dispersion liquid preparation example 10-2, use 20% メ ト ロ one ズ (Metolose) 60SH03 aqueous solution 12g and 20% デ モ one Le T aqueous solution 12g to replace 20% go one セ ラ Application (Gohseran) L3266 aqueous solution 30g, the water that adds is 66g, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 24]
In embodiment 23, use 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-t-butyl) sodium phosphate (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) F-85) replaces magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 25]
In embodiment 23, use calcium carbonate (Bai Shi カ Le シ ウ system industry system カ Le ラ イ ト KT) to replace magnesium silicate, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 26]
In embodiment 23, use calcium sulfate (with the pure pharmaceutical worker's industry of light reagent) to replace magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 27]
In embodiment 23, use titanium oxide (titanium industry system KA15) to replace magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 28]
In embodiment 13, use silica (pure pharmaceutical worker already makes with light) to replace the magnesium silicate of dispersion liquid preparation example 10-2 preparation, in addition, carry out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with Same Way.The result is as shown in table 2.
[embodiment 29]
In embodiment 23, use silica (pure pharmaceutical worker already makes with light) to replace magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 30]
In embodiment 13, remove the heat treatment step of UU and magnesium silicate dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 31]
In embodiment 14, remove the heat treatment step of UU and magnesia dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 32]
In embodiment 15, remove the heat treatment step of UU and magnesium carbonate dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 33]
In embodiment 16, remove the heat treatment step of UU and magnesium phosphate dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 34]
In embodiment 17, remove the heat treatment step of UU and magnesium hydroxide dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 35]
In embodiment 18, remove the heat treatment step of UU and alumina fluid dispersion, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 36]
In embodiment 19, remove the heat treatment step of UU and calcium silicates dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 37]
In embodiment 20, remove the heat treatment step that UU and calcium carbonate disperse liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 38]
In embodiment 21, remove the heat treatment step of UU and calcium sulfate dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 39]
In embodiment 22, remove the heat treatment step of UU and titanium oxide dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 40]
In embodiment 28, remove the heat treatment step of UU and silica dispersions, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[embodiment 41]
In embodiment 29, remove the heat treatment step of UU and silica dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[comparative example 1]
In embodiment 1, remove the heating treatment step of UU dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[comparative example 2]
In embodiment 2, remove the heating treatment step of UU dispersion liquid, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 2.
[table 2]
Figure C20048003117400501
Figure C20048003117400511
Evaluation method and evaluation criterion
1) whiteness (W) of the not Printing Department (background) before and after the humidity test of mensuration electrothermal sensitive recording paper (placing 24 hours under 40 ℃ * 90%RH environment) is according to the improved effect of its variable quantity (Δ W) evaluation moisture-proof background fog.
Zero: moisture-proof photographic fog improved effect is (Δ W is for being no more than 3) significantly
△: suitable moisture-proof photographic fog improved effect (Δ W is greater than 3 and is no more than 10) is arranged
*: slight moisture-proof photographic fog improved effect (Δ W is greater than 10 and is no more than 15) is arranged
* *: do not have moisture-proof photographic fog improved effect (Δ W is greater than 15)
2) whiteness (W) of the dispersion liquid before and after the mensuration accelerated test is according to the performance of the painted inhibitor of its variable quantity (Δ W) evaluation.
Zero: suppress whiteness and reduce effect significantly (Δ W is for being no more than 5)
△: have suitable inhibition whiteness to reduce effect (Δ W is greater than 5 and is no more than 10)
*: there is slight inhibition whiteness to reduce effect (Δ W is greater than 10 and is no more than 15)
* *: do not suppressed whiteness and reduced effect (Δ W is greater than 15)
3) L3266: go one セ ラ Application L3266 (PVA of sulfonic acid modified, Japanese synthetic chemistry system)
4) 60SH03/T: use メ ト ロ one ズ 60SH03 (hydroxypropyl methylcellulose, SHIN-ETSU HANTOTAI's chemical industry system) and デ モ one Le T (beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt, flower king system) simultaneously
[embodiment 42]
In embodiment 13, use 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-37) replaces magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 43]
In embodiment 13, use 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-43) replaces magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 44]
In embodiment 13, use three (2,6-dimethyl-4-the tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-48) replaces magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 45]
In embodiment 23, use 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-37) replaces magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 46]
In embodiment 23, use 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-43) replaces magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 47]
In embodiment 23, use three (2,6-dimethyl-4-the tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-48) replaces magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 48]
In embodiment 13, use acetoacetanilide (Samsung chemistry system) to replace magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 49]
In embodiment 13, use acetoacetyl to replace magnesium silicate for meta-xylene amine (Samsung chemistry system), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 50]
In embodiment 13, use acetoacetyl to replace magnesium silicate for ortho-aminotoluene (Samsung chemistry system), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 51]
In embodiment 23, use acetoacetanilide (Samsung chemistry system) to replace magnesium silicate, in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 52]
In embodiment 23, use acetoacetyl to replace magnesium silicate for meta-xylene amine (Samsung chemistry system), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 53]
In embodiment 23, use acetoacetyl to replace magnesium silicate for ortho-aminotoluene (Samsung chemistry system), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 54]
In embodiment 3, do not carry out the heat treated of UU dispersion liquid, in addition, use 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-37) dispersion liquid replaces the magnesium silicate dispersion liquid among the embodiment 3, and this dispersion liquid is not carried out heat treated, make its UU/DH37=10/5 (solid constituent ratio), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 55]
In embodiment 3, do not carry out the heat treated of UU dispersion liquid, in addition, use 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-43) dispersion liquid replaces the magnesium silicate dispersion liquid among the embodiment 3, and this dispersion liquid is not carried out heat treated, make its UU/DH43=10/5 (solid constituent ratio), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 56]
In embodiment 3, do not carry out the heat treated of UU dispersion liquid, in addition, use three (2,6-dimethyl-4-the tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-48) dispersion liquid replaces the magnesium silicate dispersion liquid among the embodiment 3, and this dispersion liquid is not carried out heat treated, make its UU/DH48=10/5 (solid constituent ratio), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 57]
In embodiment 3, do not carry out the heat treated of UU dispersion liquid, in addition, use acetoacetanilide (Samsung chemistry system) dispersion liquid to replace the magnesium silicate dispersion liquid among the embodiment 3, and this dispersion liquid is not carried out heat treated, make its UU/ acetoacetanilide=10/5 (solid constituent ratio), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 58]
In embodiment 3, do not carry out the heat treated of UU dispersion liquid, in addition, use acetoacetyl to replace the magnesium silicate dispersion liquid among the embodiment 3 for meta-xylene amine (Samsung chemistry system) dispersion liquid, and this dispersion liquid is not carried out heat treated, make its UU/ acetoacetyl for meta-xylene amine=10/5 (solid constituent ratio), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[embodiment 59]
In embodiment 3, do not carry out the heat treated of UU dispersion liquid, in addition, use acetoacetyl to replace the magnesium silicate dispersion liquid among the embodiment 3 for ortho-aminotoluene (Samsung chemistry system) dispersion liquid, and this dispersion liquid is not carried out heat treated, make its UU/DH37=10/5 (solid constituent ratio), in addition, carry out the preparation of dispersion liquid with Same Way, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition.The result is as shown in table 3.
[table 3]
Figure C20048003117400561
Evaluation method and evaluation criterion
1) whiteness (W) of the not Printing Department (background) before and after the humidity test of mensuration electrothermal sensitive recording paper (placing 24 hours under 40 ℃ * 90%RH environment) is according to the improved effect of its variable quantity (Δ W) evaluation moisture-proof background fog.
Zero: moisture-proof photographic fog improved effect is (Δ W is for being no more than 3) significantly
△: suitable moisture-proof photographic fog improved effect (Δ W is greater than 3 and is no more than 10) is arranged
*: slight moisture-proof photographic fog improved effect (Δ W is greater than 10 and is no more than 15) is arranged
* *: do not have moisture-proof photographic fog improved effect (Δ W is greater than 15)
2) whiteness (W) of the dispersion liquid before and after the mensuration accelerated test is according to the performance of the painted inhibitor of its variable quantity (Δ W) evaluation.
Zero: suppress whiteness and reduce effect significantly (Δ W is for being no more than 5)
△: have suitable inhibition whiteness to reduce effect (Δ W is greater than 5 and is no more than 10)
*: there is slight inhibition whiteness to reduce effect (Δ W is greater than 10 and is no more than 15)
* *: do not suppressed whiteness and reduced effect (Δ W is greater than 15)
3) L3266: go one セ ラ Application L3266 (PVA of sulfonic acid modified, Japanese synthetic chemistry system)
4) 60SH03/T: use メ ト ロ one ズ 60SH03 (hydroxypropyl methylcellulose, SHIN-ETSU HANTOTAI's chemical industry system) and デ モ one Le T (beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt, flower king system) simultaneously
[embodiment 60]
Being 15 parts by the ODB2 of dispersion liquid preparation example 1 preparation (all is the stem body standard.As follows), the UU of the common heat treatment dispersion liquid of the UU of dispersion liquid preparation example 10-1 preparation and magnesium silicate is that the D-8 of 15 parts and 1.5 parts of magnesium silicates, 3 preparations of dispersion liquid preparation example is that 15 parts, the BON of dispersion liquid preparation example 11-2 preparation are that 30 parts, the calcium carbonate of dispersion liquid preparation example 12 preparations are 20 parts, to also have zinc stearate (Zhong jing grease system Ha イ De リ Application (Hidorin) Z-7-30) be 10 parts, also have polyvinyl alcohol (Network ラ レ system Port バ one Le PVA110 is prepared into the use of 15% aqueous solution) to be that 10 parts ratio cooperates, mixes, and obtains applying liquid.
Should apply liquid with scraping strip coating machine is coated in and has 50g/m 2On the body paper of basic weight, handle with supercalender dry back, obtains electrothermal sensitive recording paper.At this moment coating amount is scaled 0.40g/m with ODB2 2
The evaluation of the moisture-proof background fog of heat-sensitive paper is carried out with following program.
The heat-sensitive paper made was placed 24 hours under 40 ℃, relative humidity 90% environment, measured the background whiteness before and after it, estimate the moisture-proof background fog of heat-sensitive paper thus.The result is shown in table 4 (table 4-1 and table 4-2).
In addition, the whiteness of dispersion composition is estimated by following program.
In the 35%ODB2 dispersion liquid of dispersion liquid preparation example 1 preparation, add distilled water diluting and become the 10%ODB2 dispersion liquid, in the 40%D-8 dispersion liquid of the 40%UU dispersion liquid of dispersion liquid preparation example 2 preparations and 3 preparations of dispersion liquid preparation example, add distilled water respectively and be diluted to 20% dispersion liquid respectively.And by mixing 10%ODB2 dispersion liquid 5g, 20%UU dispersion liquid 2.5g, 20%D-8 dispersion liquid 2.5g, the preparation dispersion composition is as estimating sample.Should estimate sample and be kept under the painted accelerated test condition and (under 40 ℃ of conditions, place 3h), measure whiteness before and after it with touch panel formula color computer-SM-T (Suga test system).Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 61]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use among the embodiment 60 is replaced with the 40%BPA dispersion liquid of dispersion liquid preparation example 4, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, equally the 40%D-8 dispersion liquid of dispersion liquid preparation example 3 is replaced with the 40%BPA dispersion liquid of dispersion liquid preparation example 4, in addition, with preparing dispersion composition as estimating sample, measure whiteness with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 62]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use among the embodiment 60 is replaced with the 40%BPS dispersion liquid of dispersion liquid preparation example 5, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, equally the 40%D-8 dispersion liquid of dispersion liquid preparation example 3 is replaced with the 40%BPS dispersion liquid of dispersion liquid preparation example 5, in addition, with preparing dispersion composition as estimating sample, measure whiteness with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 63]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use among the embodiment 60 is replaced with 40%2 of dispersion liquid preparation example 6,4 '-BPS dispersion liquid, in addition, usefulness and embodiment 60 same methods cooperate, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, the 40%D-8 dispersion liquid with dispersion liquid preparation example 3 replaces with 40%2 of dispersion liquid preparation example 6 equally, 4 '-BPS dispersion liquid, in addition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure whiteness.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 64]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use among the embodiment 60 is replaced with the 40%TGSA dispersion liquid of dispersion liquid preparation example 7, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, equally the 40%D-8 dispersion liquid of dispersion liquid preparation example 3 is replaced with the 40%TGSA dispersion liquid of dispersion liquid preparation example 7, in addition, with preparing dispersion composition as estimating sample, measure whiteness with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 65]
What use dispersion liquid preparation example 10-1 among the embodiment 60 is 70 ℃, the common heat treatment dispersion liquid for preparing under as the 6h condition of heat treatment time altogether in heat treatment temperature altogether, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure its whiteness.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 66]
Use 20% メ ト ロ one ズ (Metolose) 60SH03 (hydroxypropyl methylcellulose, SHIN-ETSU HANTOTAI's chemical industry system) aqueous solution 12g, 20% デ モ, one Le T (beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt, flower king system) aqueous solution 12g, distilled water 66g disperses the 40%UU dispersion liquid that forms (the nonvolatile component containing ratio is 43.2%; Describe the UU containing ratio in detail and be 40%, dispersant 60SH03 containing ratio is 1.6%, dispersant デ モ one Le (Demol) T containing ratio is 1.6%), the dispersant L3266 of the dispersion liquid preparation example 2 that replacement is used when preparation dispersion liquid preparation example 10-1, preparation is the heat treatment dispersion liquid altogether.With cooperating heat treatment dispersion liquid altogether with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure its whiteness.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 67]
(the nonvolatile component containing ratio is 43.2% to use 20% メ ト ロ one ズ (Metolose) 60SH03 aqueous solution 12g, 20% デ モ, one Le EP (polyocarboxy acid type high molecular surfactant, flower king system) aqueous solution 12g, distilled water 66g to disperse the 40%UU dispersion liquid that forms; Describe the UU containing ratio in detail and be 40%, dispersant 60SH03 containing ratio is 1.6%, dispersant デ モ one Le (Demol) EP containing ratio is 1.6%), the dispersant L3266 of the dispersion liquid preparation example 2 that replacement is used when preparation dispersion liquid preparation example 10-1, preparation is the heat treatment dispersion liquid altogether.With cooperating heat treatment dispersion liquid altogether with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure its whiteness.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 68]
In embodiment 60, the UU that makes the common heat treatment dispersion liquid of the UU of dispersion liquid preparation example 10-1 preparation and magnesium silicate is that 9 parts and magnesium silicate are that 0.9 part, the D-8 of dispersion liquid preparation example 3 preparations are 21 parts, the blend ratio of developer is (a) composition/(c) composition=3/7 (a solid constituent ratio), in addition, using the same method applies the preparation of liquid, carries out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure whiteness.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 69]
In embodiment 60, the UU that makes the common heat treatment dispersion liquid of the UU of dispersion liquid preparation example 10-1 preparation and magnesium silicate is that 21 parts and magnesium silicate are that 2.1 parts, the D-8 of dispersion liquid preparation example 3 preparations are 9 parts, the blend ratio of developer is (a) composition/(c) composition=7/3 (a solid constituent ratio), in addition, using the same method applies the preparation of liquid, carries out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure whiteness.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 70]
In embodiment 61, the UU that makes the common heat treatment dispersion liquid of the UU of dispersion liquid preparation example 10-1 preparation and magnesium silicate is that 9 parts and magnesium silicate are that 0.9 part, the BPA of dispersion liquid preparation example 4 preparations are 21 parts, the blend ratio of developer is (a) composition/(c) composition=3/7 (a solid constituent ratio), in addition, using the same method applies the preparation of liquid, carries out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 61 same methods prepare dispersion composition as estimating sample, measure whiteness.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 71]
In the ODB2 of dispersion liquid preparation example 1 preparation is that the UU of the common heat treatment dispersion liquid of 15 parts, the UU of dispersion liquid preparation example 10-1 preparation and magnesium silicate is that 30 parts and magnesium silicate are that 3 parts, the POB of dispersion liquid preparation example 8 preparations are that 30 parts, the calcium carbonate of dispersion liquid preparation example 12 preparations are 20 parts, to also have zinc stearate (Zhong jing grease system Ha イ De リ Application (Hidorin) Z-7-30) be 10 parts, also have polyvinyl alcohol (Network ラ レ system Port バ one Le PVA110 is prepared into the use of 15% aqueous solution) to be that 10 parts ratio cooperates, mixes, and obtains applying liquid.
Should apply liquid with scraping strip coating machine is coated in and has 50g/m 2On the body paper of basic weight, handle with supercalender dry back, obtains electrothermal sensitive recording paper.At this moment coating amount is scaled 0.40g/m with ODB2 2
The evaluation of the moisture-proof background fog of heat-sensitive paper is used and embodiment 60 same programs are carried out.Evaluation result is as shown in table 4.
In addition, the making of dispersion composition and measuring brightness carry out with following program.
In the 35%ODB2 dispersion liquid of dispersion liquid preparation example 1 preparation, add distilled water diluting and become the 10%ODB2 dispersion liquid, in the 40%POB dispersion liquid of the 40%UU dispersion liquid of dispersion liquid preparation example 2 preparations and 8 preparations of dispersion liquid preparation example, add distilled water respectively and be diluted to 20% dispersion liquid respectively.And, by mixing 10%ODB2 dispersion liquid 3g, 20%UU dispersion liquid 3g, 20%POB dispersion liquid 3g, appending distilled water 1g and prepare dispersion composition, as estimating sample.Should estimate sample and be kept under the painted accelerated test condition, measure the whiteness of its front and back with touch panel formula color computer-SM-T (Suga test system).Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 72]
Use 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-t-butyl) sodium phosphate (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) F-85) replaces dispersion liquid preparation example 10-1 magnesium silicate that use, dispersion liquid preparation example 9-1, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 73]
Use three (2,6-dimethyl-4-the tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester (rising sun electrification system ア デ カ ア one Network Le ズ (ADK Arkls) DH-48) replaces dispersion liquid preparation example 10-1 magnesium silicate that use, dispersion liquid preparation example 9-1, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 74]
Use titanium oxide (titanium industry system KA15) to replace dispersion liquid preparation example 10-1 magnesium silicate that use, dispersion liquid preparation example 9-1, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 75]
Use calcium carbonate (Bai Shi カ Le シ ウ system industry system カ Le ラ イ ト KT) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 76]
Use calcium sulfate (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 77]
Use magnesia (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 78]
Use magnesium carbonate (refreshing island chemical industry system Venus) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 79]
Use magnesium phosphate (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 80]
Use magnesium hydroxide (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 81]
Use aluminium oxide (STREM CHEMICALS reagent) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 82]
Use calcium silicates (with the pure pharmaceutical worker's industry of light reagent) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 83]
Use talcum ミ Network ロ エ ス P-4 (Japanese talcum system) to replace the magnesium silicate of the dispersion liquid preparation example 9-1 of dispersion liquid preparation example 10-1 use, in addition, with carrying out the preparation of dispersion liquid, carry out the mensuration of the whiteness of the evaluation of moisture-proof background fog of heat-sensitive paper and dispersion composition with embodiment 60 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 84]
Being 15 parts by the ODB2 of dispersion liquid preparation example 1 preparation (all is the stem body standard.As follows), the UU of the common heat treatment dispersion liquid of the UU of dispersion liquid preparation example 13 preparation and magnesium silicate is that 15 parts and magnesium silicate are that 1.5 parts, the D-8 of dispersion liquid preparation example 3 preparations are that 15 parts, the BON of dispersion liquid preparation example 11-2 preparation are that 30 parts, the calcium carbonate of dispersion liquid preparation example 12 preparations are 20 parts, to also have zinc stearate (Zhong jing grease system Ha イ De リ Application (Hidorin) Z-7-30) be 10 parts, also have polyvinyl alcohol (Network ラ レ system Port バ one Le PVA110 is prepared into the use of 15% aqueous solution) to be that 10 parts ratio cooperates, mixes, and obtains applying liquid.
The evaluation of the moisture-proof background fog of heat-sensitive paper and the measuring brightness of dispersion composition are used and embodiment 60 same methods are carried out.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 85]
When the dispersion liquid of the dispersion liquid preparation example 10-1 for preparing embodiment 60, mixed 20% magnesium silicate dispersion liquid 60g (UU solid constituent amount/magnesium silicate solid constituent amount=100/5) with respect to 40%UU dispersion liquid 600g, in addition, with 60 same method preparations apply liquid with embodiment, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.With regard to the measuring brightness of dispersion composition, when the dispersion liquid of preparation dispersion liquid preparation example 10-1, use the above-mentioned common heat treatment dispersion liquid of UU solid constituent amount/magnesium silicate solid constituent amount=100/5, in addition, usefulness and embodiment 60 same methods are carried out.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.Printing sensitivity is zero, and good, moisture-proof background fog, dispersion composition whiteness all are △.
[embodiment 86]
When the dispersion liquid of the dispersion liquid preparation example 10-1 for preparing embodiment 60, mixed 20% magnesium silicate dispersion liquid 540g (UU solid constituent amount/magnesium silicate solid constituent amount=100/45) with respect to 40%UU dispersion liquid 600g, in addition, with 60 same method preparations apply liquid with embodiment, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.With regard to the measuring brightness of dispersion composition, when the dispersion liquid of preparation dispersion liquid preparation example 10-1, use the above-mentioned common heat treatment dispersion liquid of UU solid constituent amount/magnesium silicate solid constituent amount=100/45, in addition, usefulness and embodiment 60 same methods are carried out.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
Printing sensitivity is that △, moisture-proof background fog are that △, dispersion composition whiteness are zero.
[embodiment 87]
In embodiment 60, remove the heat treatment step of magnesium silicate dispersion liquid, in addition, use the same method and carry out the preparation of dispersion liquid, carry out the evaluation of moisture-proof background fog of heat-sensitive paper and the measuring brightness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 88]
The dispersion liquid preparation example 10-1 that uses among the embodiment 60 is not carried out common heat treatment, in addition, with and same methods preparation coating liquid, the making heat-sensitive paper of embodiment 60, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, dispersion liquid preparation example 10-1 is not carried out common heat treatment, in addition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure whiteness.The evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition are used and embodiment 60 same methods are estimated.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 89]
The dispersion liquid preparation example 10-1 that uses among the embodiment 61 is not carried out common heat treatment, in addition, with and same methods preparation coating liquid, the making heat-sensitive paper of embodiment 61, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, dispersion liquid preparation example 10-1 is not carried out common heat treatment, in addition, usefulness and embodiment 61 same methods prepare dispersion composition as estimating sample, measure whiteness.The evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition are used and embodiment 60 same methods are estimated.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 90]
The dispersion liquid preparation example 10-1 that uses among the embodiment 62 is not carried out common heat treatment, in addition, with and same methods preparation coating liquid, the making heat-sensitive paper of embodiment 62, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, dispersion liquid preparation example 10-1 is not carried out common heat treatment, in addition, usefulness and embodiment 62 same methods prepare dispersion composition as estimating sample, measure whiteness.The evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition are used and embodiment 60 same methods are estimated.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 91]
The dispersion liquid preparation example 10-1 that uses among the embodiment 63 is not carried out common heat treatment, in addition, with and same methods preparation coating liquid, the making heat-sensitive paper of embodiment 63, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, dispersion liquid preparation example 10-1 is not carried out common heat treatment, in addition, usefulness and embodiment 63 same methods prepare dispersion composition as estimating sample, measure whiteness.The evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition are used and embodiment 60 same methods are estimated.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 92]
The dispersion liquid preparation example 10-1 that uses among the embodiment 64 is not carried out common heat treatment, in addition, with and same methods preparation coating liquid, the making heat-sensitive paper of embodiment 64, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, dispersion liquid preparation example 10-1 is not carried out common heat treatment, in addition, usefulness and embodiment 64 same methods prepare dispersion composition as estimating sample, measure whiteness.The evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition are used and embodiment 60 same methods are estimated.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 93]
In embodiment 66, UU is dispersed to メ ト ロ one ズ (Metolose) 60SH03 (hydroxypropyl methylcellulose, SHIN-ETSU HANTOTAI's chemical industry system) and デ モ one Le T (beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt, flower king system) after UU dispersion liquid that forms in the mixed dispersant and magnesium silicate dispersion liquid mix, do not carry out common heat treatment, the preparation dispersion liquid, in addition, with 66 same method preparations apply liquid, make heat-sensitive paper with embodiment, carry out the evaluation of its moisture-proof background fog.In addition, whiteness about dispersion composition, use is dispersed to UU does not carry out the dispersion liquid that common heat treatment is made after the UU dispersion liquid that forms in the mixed dispersant of メ ト ロ one ズ (Metolose) 60SH03 and デ モ one Le T and magnesium silicate dispersion liquid mix, in addition, with preparing dispersion composition as estimating sample, measure whiteness with embodiment 66 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 94]
In embodiment 67, UU is dispersed to メ ト ロ one ズ (Metolose) 60SH03 (hydroxypropyl methylcellulose, SHIN-ETSU HANTOTAI's chemical industry system) and デ モ one Le EP (polyocarboxy acid type high molecular surfactant, flower king system) after mixing, UU dispersion liquid that forms in the mixed dispersant and magnesium silicate dispersion liquid do not carry out common heat treatment, the preparation dispersion liquid, in addition, usefulness and embodiment 67 same methods preparations apply liquid, make heat-sensitive paper, carry out the evaluation of its moisture-proof background fog.
In addition, whiteness about dispersion composition, use is dispersed to UU does not carry out the dispersion liquid that common heat treatment is made after the UU dispersion liquid that forms in the mixed dispersant of メ ト ロ one ズ (Metolose) 60SH03 and デ モ one Le EP and magnesium silicate dispersion liquid mix, in addition, with preparing dispersion composition as estimating sample, measure whiteness with embodiment 67 same methods.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 95]
In embodiment 71, mixed dispersion liquid to UU and magnesium silicate (ト ミ AD-600, rich field pharmacy system) is not carried out common heat treatment, in addition, with carrying out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper with embodiment 71 same methods.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and magnesium silicate is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 71 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 96]
In embodiment 74, the mixed dispersion liquid of UU and titanium oxide (titanium industry system KA15) is not carried out common heat treatment, in addition, usefulness and embodiment 74 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and titanium oxide is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 74 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 97]
In embodiment 75, mixed dispersion liquid to UU and calcium carbonate (Bai Shi カ Le シ ウ system industry system カ Le ラ イ ト KT) is not carried out common heat treatment, in addition, usefulness and embodiment 75 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and calcium carbonate is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 75 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 98]
In embodiment 76, the mixed dispersion liquid of UU and calcium sulfate (with the pure pharmaceutical worker's industry of light reagent) is not carried out common heat treatment, in addition, usefulness and embodiment 76 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and calcium sulfate is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 76 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 99]
In embodiment 77, the mixed dispersion liquid of UU and magnesia (with the pure pharmaceutical worker's industry of light reagent) is not carried out common heat treatment, in addition, usefulness and embodiment 77 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition,, UU and magnesian mixed dispersion liquid are not carried out common heat treatment are prepared about the whiteness of dispersion composition, in addition, with and the whiteness of the same methods mensuration dispersion composition of embodiment 77.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 100]
In embodiment 78, the mixed dispersion liquid of UU and magnesium carbonate (refreshing island chemical industry system Venus) is not carried out common heat treatment, in addition, usefulness and embodiment 78 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and magnesium carbonate is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 78 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 101]
In embodiment 79, the mixed dispersion liquid of UU and magnesium phosphate (with the pure pharmaceutical worker's industry of light reagent) is not carried out common heat treatment, in addition, usefulness and embodiment 79 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and magnesium phosphate is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 79 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 102]
In embodiment 80, the mixed dispersion liquid of UU and magnesium hydroxide (with the pure pharmaceutical worker's industry of light reagent) is not carried out common heat treatment, in addition, usefulness and embodiment 80 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and magnesium hydroxide is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 80 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 103]
In embodiment 81, the mixed dispersion liquid of UU and aluminium oxide (STREM CHEMICALS reagent) is not carried out common heat treatment, in addition, usefulness and embodiment 81 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and aluminium oxide is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 81 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 104]
In embodiment 82, the mixed dispersion liquid of UU and calcium silicates (with the pure pharmaceutical worker's industry of light reagent) is not carried out common heat treatment, in addition, usefulness and embodiment 82 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and calcium silicates is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 82 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 105]
In embodiment 83, mixed dispersion liquid to UU and talcum ミ Network ロ エ one ス P-4 (Japanese talcum system) is not carried out common heat treatment, in addition, usefulness and embodiment 83 same methods are carried out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the mixed dispersion liquid of UU and talcum ミ Network ロ エ one ス P-4 is not carried out common heat treatment be prepared, in addition, usefulness and embodiment 83 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[embodiment 106]
The UU of dispersion liquid preparation example 13 preparations used among the embodiment 84 and the common grinding dispersion liquid of magnesium silicate are not carried out common heat treatment, in addition, with and embodiment 84 same methods carry out the preparation of dispersion liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.
In addition, about the whiteness of dispersion composition, the UU of dispersion liquid preparation example 13 preparations and the common grinding dispersion liquid of magnesium silicate are not carried out common heat treatment, in addition, usefulness and embodiment 84 same methods are measured the whiteness of dispersion composition.Contain heat treatment temperature, time conditions and the evaluation result of UU dispersion composition, as shown in table 4.
[comparative example 3]
In the ODB2 of dispersion liquid preparation example 1 preparation is that 15 parts, the UU dispersion liquid of dispersion liquid preparation example 2 preparations are that 15 parts, the D-8 of dispersion liquid preparation example 3 preparations are that 15 parts, the BON of dispersion liquid preparation example 11-2 preparation are that 30 parts, the calcium carbonate of dispersion liquid preparation example 12 preparations are 20 parts, to also have zinc stearate (Zhong jing grease system Ha イ De リ Application (Hidorin) Z-7-30) be 10 parts, also have polyvinyl alcohol (Network ラ レ system Port バ one Le PVA110 is prepared into the use of 15% aqueous solution) to be that 10 parts ratio cooperates, mixes, and obtains applying liquid.
Should apply liquid with scraping strip coating machine is coated in and has 50g/m 2On the body paper of basic weight, handle with supercalender dry back, obtains electrothermal sensitive recording paper.At this moment coating amount is scaled 0.40g/m with ODB2 2
About the evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition, use the non-heat treated UU dispersion liquid of dispersion liquid preparation example 2 replace dispersion liquid preparation example 10-1 as the UU dispersion liquid, in addition, usefulness and embodiment 60 same methods are estimated.Evaluation result is as shown in table 4.
[comparative example 4]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use in the comparative example 3 is replaced to the 40%BPA dispersion liquid of dispersion liquid preparation example 4, in addition, with 3 same method preparations apply liquid, make heat-sensitive paper with comparative example, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, equally the 40%D-8 dispersion liquid of dispersion liquid preparation example 3 is replaced to the 40%BPA dispersion liquid of dispersion liquid preparation example 4, in addition, with preparing dispersion composition as estimating sample, measure whiteness with comparative example 3 same methods.About the evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition, with and embodiment 60 same methods estimate.Evaluation result is as shown in table 4.
[comparative example 5]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use in the comparative example 3 is replaced to the 40%BPS dispersion liquid of dispersion liquid preparation example 5, in addition, with 3 same method preparations apply liquid, make heat-sensitive paper with comparative example, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, equally the 40%D-8 dispersion liquid of dispersion liquid preparation example 3 is replaced to the 40%BPS dispersion liquid of dispersion liquid preparation example 5, in addition, with preparing dispersion composition as estimating sample, measure whiteness with comparative example 3 same methods.About the evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition, with and embodiment 60 same methods estimate.Evaluation result is as shown in table 4.
[comparative example 6]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use in the comparative example 3 is replaced to 40%2 of dispersion liquid preparation example 6,4 '-BPS dispersion liquid, in addition, usefulness and comparative example 3 same methods preparations apply liquid, make heat-sensitive paper, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, the 40%D-8 dispersion liquid with dispersion liquid preparation example 3 replaces to 40%2 of dispersion liquid preparation example 6 equally, 4 '-BPS dispersion liquid, in addition, usefulness and comparative example 3 same methods prepare dispersion composition as estimating sample, measure whiteness.About the evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition, with and embodiment 60 same methods estimate.Evaluation result is as shown in table 4.
[comparative example 7]
The 40%D-8 dispersion liquid of the dispersion liquid preparation example 3 of use in the comparative example 3 is replaced to the 40%TGSA dispersion liquid of dispersion liquid preparation example 7, in addition, with 3 same method preparations apply liquid, make heat-sensitive paper with comparative example, carry out the evaluation of its moisture-proof background fog.In addition, about the whiteness of dispersion composition, equally the 40%D-8 dispersion liquid of dispersion liquid preparation example 3 is replaced to the 40%TGSA dispersion liquid of dispersion liquid preparation example 7, in addition, with preparing dispersion composition as estimating sample, measure whiteness with comparative example 3 same methods.About the evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition, with and embodiment 60 same methods estimate.Evaluation result is as shown in table 4.
[comparative example 8]
In embodiment 66, only UU is dispersed to メ ト ロ one ズ (Metolose) 60SH03 (hydroxypropyl methylcellulose, SHIN-ETSU HANTOTAI's chemical industry system) and デ モ one Le T (beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt, flower king system) in the dispersant that mixes, do not mix UU dispersion liquid and magnesium silicate dispersion liquid, and do not heat-treat preparation UU dispersion liquid.With this non-heat treatment UU dispersion liquid with and embodiment 60 same methods cooperate, preparation coating liquid, the making heat-sensitive paper carries out the evaluation of its moisture-proof background fog.In addition, whiteness about dispersion composition, as the UU dispersion liquid, use and only UU to be dispersed in the dispersant that メ ト ロ one ズ (Metolose) 60SH03 and デ モ one Le T mix, do not mix UU dispersion liquid and magnesium silicate dispersion liquid, and the UU dispersion liquid of not heat-treating, in addition, with preparing dispersion composition as estimating sample, measure whiteness with embodiment 60 same methods.About the evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition, with and embodiment 60 same methods estimate.Evaluation result is as shown in table 4.
[comparative example 9]
In embodiment 67, only UU is dispersed to メ ト ロ one ズ (Metolose) 60SH03 (hydroxypropyl methylcellulose, SHIN-ETSU HANTOTAI's chemical industry system) and デ モ one Le EP (polyocarboxy acid type high molecular surfactant, flower king system) in the dispersant that mixes, do not mix UU dispersion liquid and magnesium silicate dispersion liquid, and do not heat-treat preparation UU dispersion liquid.With this non-heat treatment UU dispersion liquid with and embodiment 60 same methods cooperate, preparation coating liquid, the making heat-sensitive paper carries out the evaluation of its moisture-proof background fog.In addition, whiteness about dispersion composition, as the UU dispersion liquid, use and only UU to be dispersed in the dispersant that メ ト ロ one ズ (Metolose) 60SH03 and デ モ one Le EP mix, do not mix UU dispersion liquid and magnesium silicate dispersion liquid, and the UU dispersion liquid of not heat-treating, in addition, with preparing dispersion composition as estimating sample, measure whiteness with embodiment 60 same methods.About the evaluation of the moisture-proof background fog of heat-sensitive paper, the whiteness of dispersion composition, with and embodiment 60 same methods estimate.Evaluation result is as shown in table 4.
[comparative example 10]
In embodiment 71, do not use the magnesium silicate dispersion liquid, the non-heat treated dispersion liquid of the UU of use dispersion liquid preparation example 2 preparations is as the UU dispersion liquid, in addition, the preparation that uses the same method applies liquid, makes heat-sensitive paper, carries out the evaluation of its moisture-proof background fog.
In addition, about the making and the measuring brightness of dispersion composition, the non-heat treated dispersion liquid of the UU of use dispersion liquid preparation example 2 preparations is as the UU dispersion liquid, and in addition, usefulness and embodiment 71 same programs are carried out.
The measurement result of heat-sensitive paper evaluation result and whiteness is as shown in table 4.
[comparative example 11]
When the dispersion liquid of the dispersion liquid preparation example 10-1 for preparing embodiment 60, mixed 20% magnesium silicate dispersion liquid 840g (UU solid constituent amount/magnesium silicate solid constituent amount=100/70) with respect to 40%UU dispersion liquid 600g, in addition, with 60 same method preparations apply liquid with embodiment, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.About the measuring brightness of dispersion composition, when the dispersion liquid of preparation dispersion liquid preparation example 10-1, use the above-mentioned common heat treatment dispersion liquid of UU solid constituent amount/magnesium silicate solid constituent amount=100/70, in addition, usefulness and embodiment 60 same methods are carried out.Since the superfluous printing of the addition of inorganic salts sensitivity for *, the moisture-proof background fog is △, shows the tendency that descends.But the whiteness of dispersion composition is zero.The result is as shown in table 4.
[table 4-1]
Figure C20048003117400771
Figure C20048003117400781
[table 4-2]
Figure C20048003117400782
Figure C20048003117400801
Evaluation method and evaluation criterion
Mark when 1) dispersion liquid of each composition being heat-treated separately: for example use, divide mark) (a) and (b)
Mark when the dispersion liquid mixing of each composition is heat-treated: usefulness+binding mark is for example) (a)+(b)
The optical concentration of the image when 2) printing sensitivity makes its colour developing with printing energy 0.51mj/dot
Zero: optical concentration value 1.0 or higher
△: optical concentration value 0.9 is to less than 1.0
*: the optical concentration value is less than 0.9
3) whiteness (W) of the not Printing Department (background) before and after the humidity test of mensuration electrothermal sensitive recording paper (placing 24 hours under 40 ℃ * 90%RH environment) is according to the improved effect of its variable quantity (Δ W) evaluation moisture-proof background fog.
Zero: moisture-proof photographic fog improved effect is (Δ W is for being no more than 5) significantly
△: moisture-proof photographic fog improved effect (Δ W is greater than 5 and is no more than 10) is arranged
*: moisture-proof photographic fog improved effect little (Δ W is greater than 10 and is no more than 20)
* *: do not have moisture-proof photographic fog improved effect (Δ W is greater than 20)
4) whiteness (W) of the dispersion liquid before and after the mensuration accelerated test is according to the performance of the painted inhibitor of its variable quantity (Δ W) evaluation.
Zero: suppress whiteness and reduce effect significantly (Δ W is for being no more than 7)
△: have the whiteness of inhibition to reduce effect (Δ W is greater than 7 and is no more than 15)
*: suppress whiteness and reduce effect little (Δ W is greater than 15 and is no more than 25)
* *: do not suppressed whiteness and reduced effect (Δ W is greater than 25)
5) 60SH/T: use メ ト ロ one ズ 60SH03 and デ モ one Le T simultaneously than 1/1 by solid constituent
6) 60SH/EP: use メ ト ロ one ズ 60SH03 and デ モ one Le EP simultaneously than 1/1 by solid constituent
[embodiment 107]
The common heat treatment temperature of the dispersion liquid preparation example 10-1 that uses among the preparation embodiment 60 is 40 ℃, heat treatment time is the common heat treatment dispersion liquid of 168h altogether, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure its whiteness.The measurement result of heat-sensitive paper evaluation result and whiteness is shown in table 5 (table 5-1 and table 5-2).
[embodiment 108]
The common heat treatment temperature of the dispersion liquid preparation example 10-1 that uses among the preparation embodiment 60 is 90 ℃, heat treatment time is the common heat treatment dispersion liquid of 3h altogether, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure its whiteness.The measurement result of heat-sensitive paper evaluation result and whiteness is as shown in table 5.Sensitivity has decline a little, but the whiteness of moisture-proof background fog, dispersion composition is zero.
[comparative example 12]
The treatment temperature of the dispersion liquid preparation example 10-1 that preparation is used among the embodiment 60 is 30 ℃, the processing time processing dispersion liquid as 168h, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure its whiteness.The measurement result of heat-sensitive paper evaluation result and whiteness is as shown in table 5.30 ℃ treatment temperature, even prolong the processing time, the moisture-proof background fog be *, the whiteness of dispersion composition also is *.
[comparative example 13]
The common heat treatment temperature of the dispersion liquid preparation example 10-1 that uses among the preparation embodiment 60 is 95 ℃, heat treatment time is the common heat treatment dispersion liquid of 3h altogether, in addition, with cooperating with embodiment 60 same methods, apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, measure its whiteness.The measurement result of heat-sensitive paper evaluation result and whiteness is as shown in table 5.95 ℃ heat treatment temperature, the whiteness of dispersion composition is good, but sensitivity significantly reduces, and is not preferred.
[table 5-1]
Figure C20048003117400821
[table 5-2]
Figure C20048003117400822
Evaluation method and evaluation criterion
Mark when 1) dispersion liquid of each composition being heat-treated separately: for example use, divide mark) (a) and (b)
Mark when the dispersion liquid mixing of each composition is heat-treated: usefulness+binding mark is for example) (a)+(b)
The optical concentration of the image when 2) printing sensitivity makes its colour developing with printing energy 0.51mj/dot
Zero: optical concentration value 1.0 or higher
△: the optical concentration value is not less than 0.9 and less than 1.0
*: the optical concentration value is less than 0.9
3) whiteness (W) of the not Printing Department (background) before and after the humidity test of mensuration electrothermal sensitive recording paper (placing 24 hours under 40 ℃ * 90%RH environment) is according to the improved effect of its variable quantity (Δ W) evaluation moisture-proof background fog.
Zero: moisture-proof photographic fog improved effect is (Δ W is for being no more than 5) significantly
△: moisture-proof photographic fog improved effect (Δ W is greater than 5 and is no more than 10) is arranged
*: moisture-proof photographic fog improved effect little (Δ W is greater than 10 and is no more than 20)
* *: do not have moisture-proof photographic fog improved effect (Δ W is greater than 20)
4) whiteness (W) of the dispersion liquid before and after the mensuration accelerated test is according to the performance of the painted inhibitor of its variable quantity (Δ W) evaluation.
Zero: suppress whiteness and reduce effect significantly (Δ W is for being no more than 7)
△: have the whiteness of inhibition to reduce effect (Δ W is greater than 7 and is no more than 15)
*: suppress whiteness and reduce effect little (Δ W is greater than 15 and is no more than 25)
* *: do not suppressed whiteness and reduced effect (Δ W is greater than 25)
[embodiment 109]
The common heat treatment dispersion liquid that uses among the preparation embodiment 60, in addition, usefulness and embodiment 60 same methods cooperate, and apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, and painted accelerated test condition is made as 3h under 50 ℃ of conditions, measure its whiteness.The heat treatment temperature, time conditions and the evaluation result that contain the UU dispersion composition are shown in table 6 (table 6-1 and table 6-2).Although painted acceleration environment has risen 10 ℃, the whiteness of dispersion composition is zero, confirms sufficient painted inhibition effect.
[embodiment 110]
In embodiment 67, only use to prepare dispersion composition at 60 ℃ of UU dispersion liquids that carried out 48 hours heat treated, do not add the magnesium silicate dispersion liquid.In addition, usefulness and embodiment 60 same methods cooperate, and apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, after painted accelerated test condition is to preserve 3h under 40 ℃ of conditions, measure its whiteness.Evaluation result is as shown in table 6.Printing sensitivity is zero, the moisture-proof background fog is zero, the whiteness of dispersion composition is zero, confirms sufficient painted inhibition effect.
[embodiment 111]
In embodiment 67, only use to prepare dispersion composition at 60 ℃ of UU dispersion liquids that carried out 48 hours heat treated, do not add the magnesium silicate dispersion liquid.In addition, usefulness and embodiment 60 same methods cooperate, and apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, after painted accelerated test condition is to preserve 3h under 50 ℃ of conditions, measure its whiteness.Evaluation result is as shown in table 6.Printing sensitivity is zero, the moisture-proof background fog is zero, the whiteness of dispersion composition is △, and can confirm: because painted acceleration environment has risen 10 ℃, the whiteness of dispersion composition descends a little.
[embodiment 112]
In embodiment 66, only use to prepare dispersion composition at 60 ℃ of UU dispersion liquids that carried out 48 hours heat treated, do not add the magnesium silicate dispersion liquid.In addition, usefulness and embodiment 60 same methods cooperate, and apply the preparation of liquid, carry out the evaluation of the moisture-proof background fog of heat-sensitive paper.In addition, about the whiteness of dispersion composition, usefulness and embodiment 60 same methods prepare dispersion composition as estimating sample, after painted accelerated test condition is to preserve 3h under 40 ℃ of conditions, measure its whiteness.Evaluation result is as shown in table 6.The whiteness that printing sensitivity is zero, the moisture-proof background fog is △, dispersion composition is △.
[table 6-1]
Figure C20048003117400851
[table 6-2]
Figure C20048003117400852
Evaluation method and evaluation criterion
Mark when 1) dispersion liquid of each composition being heat-treated separately: for example use, divide mark) (a) and (b)
Mark when the dispersion liquid mixing of each composition is heat-treated: usefulness+binding mark is for example) (a)+(b)
The optical concentration of the image when 2) printing sensitivity makes its colour developing with printing energy 0.51mj/dot
Zero: optical concentration value 1.0 or higher
△: optical concentration value 0.9 or higher and less than 1.0
*: the optical concentration value is less than 0.9
3) whiteness (W) of the not Printing Department (background) before and after the humidity test of mensuration electrothermal sensitive recording paper (placing 24 hours under 40 ℃ * 90%RH environment) is according to the improved effect of its variable quantity (Δ W) evaluation moisture-proof background fog.
Zero: moisture-proof photographic fog improved effect is (Δ W is for being no more than 5) significantly
△: moisture-proof photographic fog improved effect (Δ W is greater than 5 and is no more than 10) is arranged
*: moisture-proof photographic fog improved effect little (Δ W is greater than 10 and is no more than 20)
* *: do not have moisture-proof photographic fog improved effect (Δ W is greater than 20)
4) whiteness (W) of the dispersion liquid before and after the mensuration accelerated test is according to the performance of the painted inhibitor of its variable quantity (Δ W) evaluation.
Zero: suppress whiteness and reduce effect significantly (Δ W is for being no more than 7)
△: have the whiteness of inhibition to reduce effect (Δ W is greater than 7 and is no more than 15)
*: suppress whiteness and reduce effect little (Δ W is greater than 15 and is no more than 25)
* *: do not suppressed whiteness and reduced effect (Δ W is greater than 25)
5) 60SH/T: use メ ト ロ one ズ 60SH03 and デ モ one Le T simultaneously than 1/1 by solid constituent
6) 60SH/EP: use メ ト ロ one ズ 60SH03 and デ モ one Le EP simultaneously than 1/1 by solid constituent
[embodiment 113]
With developer UU52.5g, メ ト ロ one ズ (Metolose) 60SH03 (hydroxypropyl methylcellulose of solid constituent 5.38%, SHIN-ETSU HANTOTAI's chemical industry system) 48.75g, デ モ one Le (Demol) T (the beta-naphthalenesulfonic-acid formaldehyde condensation compound sodium salt of solid constituent 5.38%, flower king system) 48.75g and the 150ml bead (Ф 0.6mm) of measuring with graduated cylinder, pack in the container of 400ml, at revolution is under the condition of 2000rpm, with sand mill (ア イ メ Star Network ス (AIMEX Co., Ltd) society's system) pulverize, disperseed 3 hours, and obtained the UU dispersion 140g of solid constituent 38.5%.This UU dispersion is packed in the 200ml flask, make with thermostat that temperature maintenance stirred 12 hours with Three-One Motor at 60 ℃ in the flask under 250rpm, carry out heat treated.The average grain diameter of the UU dispersion after the heat treatment is 0.46 μ m.
In addition, go one セ ラ Application (Gohseran) L3266 (PVA of sulfonic acid modified with the 3-dibutylamino-6-methyl-7-anilino fluorane of dyestuff (below be designated as ODB2) 52.5g, solid constituent 5.38%, Japan's synthetic chemistry system) aqueous solution 97.5g and the 150ml bead (Ф 0.6mm) of measuring with graduated cylinder, pack in the container of 400ml, at revolution is under the condition of 2000rpm, with sand mill (ア イ メ Star Network ス (AIMEX Co., Ltd) society's system) pulverized, disperse 3 hours, obtain the ODB2 dispersion of solid constituent 38.5%.This ODB2 dispersion is packed in the 200ml flask, make with thermostat that temperature maintenance stirred 24 hours with Three-One Motor at 40 ℃ in the flask under 250rpm, carry out heat treated.The average grain diameter of the ODB2 dispersion after the heat treatment is 0.49 μ m.
In addition, go one セ ラ Application (Gohseran) L3266 (PVA of sulfonic acid modified with sensitizer diphenyl sulphone (DPS) (below be designated as DP) 52.5g, solid constituent 5.38%, Japan's synthetic chemistry system) aqueous solution 97.5g and the 150ml bead (Ф 0.6mm) of measuring with graduated cylinder, pack in the container of 400ml, at revolution is under the condition of 2000rpm, (ア イ メ Star Network ス (AIMEX Co., Ltd) society's system) pulverized, disperses 3 hours, obtained the DP dispersion of solid constituent 38.5% with sand mill.The average grain diameter of the DP dispersion that at this moment obtains is 0.60 μ m.
In addition, calcium carbonate 10g and water 30g are mixed, carry out dispersed with stirring, obtain dispersion with agitator.
The evaluation of the moisture-proof background fog of heat-sensitive paper is undertaken by following program.
With these dispersions in drying solid composition 20 weight portions of drying solid composition 30 weight portions of drying solid composition 15 weight portions of drying solid composition 30 weight portions of above-mentioned UU dispersion, ODB2 dispersion, DP dispersion, a divided calcium carbonate prose style free from parallelism, also have solid component concentration be the zinc stearate dispersion of 16 weight % drying solid composition 10 weight portions, also have the ratio (stem body standard) of drying solid composition 10 weight portions of 15 weight % polyvinyl alcohol to mix, obtain applying liquid.
Should apply liquid with scraping strip coating machine is coated in and has 50g/m 2On the body paper of basic weight, handle with supercalender dry back, obtains electrothermal sensitive recording paper.At this moment coating amount is scaled 0.40g/m with ODB2 2
On the heat-sensitive paper that makes like this, print applying under voltage 24V, the pulse width 1.5msec condition, by being determined at the background whiteness of placing under the 40 ℃ * 90%RH environment after 24 hours, estimate its moisture-proof background fog.The evaluation result that whiteness changes (Δ W) is zero.
In addition, the whiteness of dispersion composition is estimated by following program.
With the ODB2 dispersion be diluted to 10% (the weight % of ODB2), the UU dispersion is diluted to 20% (the weight % of UU), making the weight ratio that contains in two kinds of mixed dispersion liquid is that ODB2/UU=1/2 mixes, sample is estimated in preparation.After measuring this whiteness, under 40 ℃ of conditions, placed 3 hours, measure whiteness once more, calculate poor (the Δ whiteness) of the whiteness of heat treatment front and back.The evaluation result of the whiteness of dispersion composition is zero.The result is shown in table 7 (table 7-1 and table 7-2).
[embodiment 114]
In embodiment 113, when making the UU dispersion, use デ モ one Le (Demol) SSL (special aromatic sulphonic acid formaldehyde condensation products sodium salt, flower king system) aqueous solution 48.75g replaces メ ト ロ one ズ (Metolose) 60SH03 as dispersant, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.49 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 115]
In embodiment 113, when making the UU dispersion, use メ ト ロ one ズ (Metolose) the 60SH03 aqueous solution 97.5g of solid constituent 5.38% as dispersant separately, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 116]
In embodiment 115, when making the UU dispersion, in addition デ モ one Le (Demol) the T aqueous solution 97.5g that uses solid constituent 5.38% separately is as dispersant,, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 117]
In embodiment 115, when making the UU dispersion, use デ モ one Le (Demol) EP (the special polyocarboxy acid type high molecular surfactant of solid constituent 5.38% separately, flower king system) aqueous solution 97.5g is as dispersant, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 118]
In embodiment 115, when making the UU dispersion, use the HPC-L (hydroxypropyl cellulose of solid constituent 5.38% separately, Japan Cao Da system) aqueous solution 97.5g is as dispersant, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.46 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 119]
In embodiment 115, when making the UU dispersion, use セ ロ ゲ Application (Cellogen) 6A (sanlose of solid constituent 5.38% separately, the first industrial pharmacy system) aqueous solution 97.5g is as dispersant, the UU dispersion is carried out the heat treatment of 50 ℃ * 24h, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.48 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 120]
In embodiment 115, when making the UU dispersion, use Network ラ レ Port バ one Le (Kuraray Poval) PVA-108 (the fully saponified type of solid constituent 5.38% separately, the degree of polymerization 300, Network ラ レ system) aqueous solution 97.5g is as dispersant, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.46 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 121]
In embodiment 115, when making the UU dispersion, use surfactant D KS デ イ ス コ one ト (Discoat) N-14 (the special polycarboxylic acids NH4 salt of solid constituent 5.38% separately, the first industrial pharmacy system) aqueous solution 97.5g is as dispersant, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 122]
In embodiment 113, sensitizer uses BON to replace DP, in addition, uses the same method and carries out the preparation of dispersion, carries out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the BON dispersion that at this moment obtains is 0.50 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 123]
In embodiment 113, sensitizer uses HS3520 to replace DP, in addition, uses the same method and carries out the preparation of dispersion, carries out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the HS3520 dispersion that at this moment obtains is 0.53 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 124]
In embodiment 113, sensitizer uses benzylbiphenyl (below be designated as PBBP) is replaced DP, in addition, uses the same method and carries out the preparation of dispersion, carries out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the PBBP dispersion that at this moment obtains is 0.51 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 125]
In embodiment 113, dyestuff uses 3-lignocaine-6-methyl-7-anilino fluorane (below be designated as ODB) to replace ODB2, in addition, uses the same method and carries out the preparation of dispersion, carries out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the ODB dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 126]
In embodiment 113, dyestuff uses 3-isopentyl ethylamino-6-methyl-7-anilino fluorane (below be designated as S205) to replace ODB2, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the S205 dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is △, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 127]
In embodiment 113, dyestuff uses 3-ethyl-p-methylphenyl amino-6-methyl-7-anilino fluorane (below be designated as ETAC) to replace ODB2, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the ETAC dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is △, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 128]
In embodiment 113, dyestuff uses 3-dibutylamino-7-(adjacent fluorine)-anilino fluorane (below be designated as TG21) to replace ODB2, in addition, uses the same method and carries out the preparation of dispersion, carries out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the TG21 dispersion that at this moment obtains is 0.48 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 129]
In embodiment 113, when making the UU dispersion, use go one セ ラ Application (Gohseran) L3266 (PVA of sulfonic acid modified, Japan's synthetic chemistry system) aqueous solution 48.75g replaces メ ト ロ one ズ (Metolose) 60SH03 as dispersant, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.49 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[embodiment 130]
In embodiment 113, when making the UU dispersion, use DKS デ イ ス コ one ト (Discoat) N-14 (special polycarboxylic acids NH4 salt, the first industrial pharmacy system) aqueous solution 48.75g replaces デ モ one Le (Demol) T as dispersant, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.49 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 131]
In embodiment 115, when making the UU dispersion, use メ ト ロ one ズ (Metolose) SM15 (methylcellulose of solid constituent 5.38% separately, SHIN-ETSU HANTOTAI's chemical industry system) aqueous solution 97.5g is as dispersant, the UU dispersion is carried out the heat treatment of 50 ℃ * 24h, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.47 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[embodiment 132]
In embodiment 113, dyestuff uses 3-diamyl amino-6-methyl-7-anilino fluorane (below be designated as BLACK305) to replace ODB2, in addition, uses the same method and carries out the preparation of dispersion, carries out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the BLACK305 dispersion that at this moment obtains is 0.49 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is zero.The result is as shown in table 7.
[comparative example 14]
In embodiment 113, the UU dispersion is not carried out heat treated, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.46 μ m.The evaluation result of moisture-proof background fog is zero, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[comparative example 15]
In embodiment 114, the UU dispersion is not carried out heat treated, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.49 μ m.The evaluation result of moisture-proof background fog is △, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[comparative example 16]
In embodiment 117, the UU dispersion is not carried out heat treated, in addition, use the same method and carry out the preparation of dispersion, carry out the whiteness evaluation of heat-sensitive paper performance, dispersion composite.The average grain diameter of the UU dispersion that at this moment obtains is 0.48 μ m.The evaluation result of moisture-proof background fog is △, and the evaluation result of the whiteness of dispersion composition is △.The result is as shown in table 7.
[table 7-1]
Figure C20048003117400941
[table 7-2]
Figure C20048003117400951
Evaluation method and evaluation criterion
Mark when 1) dispersion liquid of each composition being heat-treated separately: for example use, divide mark) (a) and (b)
Mark when the dispersion liquid mixing of each composition is heat-treated: usefulness+binding mark is for example) (a)+(b)
The optical concentration of the image when 2) printing sensitivity makes its colour developing with printing energy 0.51mj/dot
Zero: optical concentration value 1.0 or higher
△: optical concentration value 0.9 or higher and less than 1.0
*: the optical concentration value is less than 0.9
3) whiteness (W) of the not Printing Department (background) before and after the humidity test of mensuration electrothermal sensitive recording paper (placing 24 hours under 40 ℃ * 90%RH environment) is according to the improved effect of its variable quantity (Δ W) evaluation moisture-proof background fog.
Zero: moisture-proof photographic fog improved effect is (Δ W is for being no more than 5) significantly
△: moisture-proof photographic fog improved effect (Δ W is greater than 5 and is no more than 10) is arranged
*: moisture-proof photographic fog improved effect little (Δ W is greater than 10 and is no more than 20)
* *: do not have moisture-proof photographic fog improved effect (Δ W is greater than 20)
4) whiteness (W) of the dispersion liquid before and after the mensuration accelerated test is according to the performance of the painted inhibitor of its variable quantity (Δ W) evaluation.
Zero: suppress whiteness and reduce effect significantly (Δ W is for being no more than 7)
△: have the whiteness of inhibition to reduce effect (Δ W is greater than 7 and is no more than 15)
*: suppress whiteness and reduce effect little (Δ W is greater than 15 and is no more than 25)
* *: do not suppressed whiteness and reduced effect (Δ W is greater than 25)
5) 60SH/T: use メ ト ロ one ズ 60SH03 and デ モ one Le T simultaneously than 1/1 by solid constituent
6) 60SH/EP: use メ ト ロ one ズ 60SH03 and デ モ one Le EP simultaneously than 1/1 by solid constituent
7) SSL/T: use デ モ one Le SSL and デ モ one Le T simultaneously than 1/1 by solid constituent
8) L3266/SSL uses L3266 and デ モ one Le SSL by solid constituent simultaneously than 1/1
9) 60SH/N14: use メ ト ロ one ズ 60SH03 and DKS デ イ ス コ one ト N14 simultaneously than 1/1 by solid constituent
[comparative example 17]
In embodiment 113, when making the UU dispersion, use コ one ミ Application (Quartamin) 24P (lauryl trimethyl ammonium chloride of solid constituent 5.38% separately, flower king system) aqueous solution 97.5g is as dispersant, in addition, use the same method and carry out the preparation of dispersion, but when mixing, solidify, do not obtain good dispersion composite with the ODB2 dispersion.
[comparative example 18]
In embodiment 113, when making the UU dispersion, use サ ニ ゾ one Le (Sanizol) C (the alkyl benzyl ammonio methacrylate of solid constituent 5.38% separately, flower king system) aqueous solution 97.5g is as dispersant, in addition, use the same method and carry out the preparation of dispersion, but when mixing, solidify, do not obtain good dispersion composite with the ODB2 dispersion.
The possibility of commercial Application
The present invention is suitable as recording materials, the particularly thermal recording medium that contains urea-carbamate compounds, the decline that its whiteness that can improve the coating liquid that contains colourless or light dyestuff former and urea-carbamate compounds is passed in time, simultaneously, can improve background fog (moisture-proof background fog) under background fog, the particularly high humidity of using the thermal recording medium that this coating liquid is made.

Claims (18)

1. the composition used of preparation Color Appearance System, it obtains by being included in to be dispersed in the liquid medium and to carry out heat treated with at least a composition a urea-carbamate compounds that has at least one urea groups and at least one carbamate groups in a part respectively.
2. composition as claimed in claim 1, wherein, at least a in the material of any expression that described composition a urea-carbamate compounds is a following formula (I)～(VI),
Figure C2004800311740002C1
Wherein, X, Y, Z represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and in addition, each residue can have substituting group;
Figure C2004800311740002C2
Wherein, X, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and in addition, each residue can have substituting group;
Figure C2004800311740002C3
Wherein, X, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and α represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer, and in addition, each residue can have substituting group;
Figure C2004800311740002C4
Wherein, Z, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and β represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer, and in addition, each residue can have substituting group;
Figure C2004800311740002C5
Wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue, and in addition, each residue can have substituting group; γ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-, following formula (a) any or represent direct key, n is 1 or 2;
Figure C2004800311740003C1
Wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue, and in addition, each residue can have substituting group; δ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-,-NH-,-CH (COOR 1)-,-C (CF 3) 2-,-CR 2R 3-any or represent direct key, wherein, R 1, R 2, R 3The expression carbon number is 1 to 20 alkyl, and n is 1 or 2.
3. composition as claimed in claim 1 or 2, it contains by described composition a urea-carbamate compounds being scattered in the liquid medium and heating available dispersion liquid being not less than under 40 ℃ the temperature.
4. the composition used of preparation Color Appearance System, it contains by being included in at least a composition a urea-carbamate compounds that has at least one urea groups and at least one carbamate groups in a part respectively, and being scattered in the dispersion liquid that forms in the liquid medium as at least a compound that is selected from silicate, carbonate, sulfate, phosphate, metal oxide, metal hydroxides, hindered phenol compound, hindered amine compound and the acetoacetate derivative of the painted inhibitor of composition b.
5. composition as claimed in claim 4, wherein, carrying out heat treated by the either party among described at least composition a and the described composition b can obtain.
6. composition as claimed in claim 4, wherein, at least a in the material of any expression that described composition a urea-carbamate compounds is a following formula (I)～(VI),
Figure C2004800311740004C1
Wherein, X, Y, Z represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and in addition, each residue can have substituting group;
Figure C2004800311740004C2
Wherein, X, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and in addition, each residue can have substituting group;
Figure C2004800311740004C3
Wherein, X, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and α represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer, and in addition, each residue can have substituting group;
Figure C2004800311740004C4
Wherein, Z, Y represent aromatic compound residue or heterocyclic compound residue or aliphatic compound residue, and β represents to have the residue of the valence mumber of divalent at least, and n represents to be not less than 2 integer, and in addition, each residue can have substituting group;
Figure C2004800311740005C1
Wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue, and in addition, each residue can have substituting group; γ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-, following formula (a) any or represent direct key, n is 1 or 2;
Wherein, the hydrogen atom of phenyl ring can be by aromatic compound residue or aliphatic compound residue or the replacement of heterocyclic compound residue, and in addition, each residue can have substituting group; δ represents-SO 2-,-O-,-(S) n-,-(CH 2) n-,-CO-,-CONH-,-NH-,-CH (COOR 1)-,-C (CF 3) 2-,-CR 2R 3-any or represent direct key, wherein, R 1, R 2, R 3The expression carbon number is 1 to 20 alkyl, and n is 1 or 2.
7. as each described composition of claim 4～6, wherein, the painted inhibitor of described composition b is to be selected from magnesium silicate, calcium silicates, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium phosphate, 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) sodium phosphate, magnesia, aluminium oxide, titanium oxide, magnesium hydroxide, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, three (2, the 6-dimethyl-4-tert-butyl group-3-hydroxybenzyl) isocyanuric acid ester, at least a in the meta-xylene amine of acetoacetanilide and acetoacetyl.
8. as claim 1 or 4 described compositions, it further contains and is selected from phenol derivatives, aromatic derivant carboxylate or its metal salt compound, salicyclic acid derivatives or its metal salt compound, N, at least a compound in N-diaryl thiourea derivative and the sulfonyl urea derivates as composition c acid developer.
9. composition as claimed in claim 8, wherein, the phenol derivatives of described composition c acid developer is to be selected from 2, two (4-hydroxy phenyl) propane of 2-, two (4-hydroxy phenyl) sulfone, 4-isopropyl oxygen base phenyl-4 '-hydroxy phenyl sulfone, 2, at least a in 4 '-dihydroxydiphenylsulisomer, two (3-pi-allyl-4-hydroxy phenyl) sulfone and the 4-Para Hydroxy Benzoic Acid benzyl ester.
10. composition as claimed in claim 4, it contains by described composition a urea-carbamate compounds being scattered in the liquid medium and heating available dispersion liquid being not less than under 40 ℃ the temperature.
11. composition as claimed in claim 4, it contains by the painted inhibitor of described composition b being scattered in the liquid medium and heating available dispersion liquid being not less than under 40 ℃ the temperature.
12. composition as claimed in claim 4, it contains by described composition a urea-carbamate compounds being scattered in the liquid medium and heating available dispersion liquid under being not less than 40 ℃ temperature, and heating available dispersion liquid by being scattered in the painted inhibitor of composition b in the liquid medium and being not less than under 40 ℃ the temperature.
13. composition as claimed in claim 4, wherein, with respect to composition a urea-carbamate compounds 100 mass parts, the amount of the painted inhibitor of described composition b is that 1 mass parts is extremely less than 50 mass parts.
14. as claim 1 or 4 described compositions, wherein, when the painted inhibitor of described composition a urea-carbamate compounds and/or composition b is disperseed, use at least a dispersant that is selected from the group that constitutes by water-soluble nonionic macromolecular compound, water soluble anion macromolecular compound, anion surfactant, non-ionic surface active agent and zwitterionic surfactant to make its dispersion.
15. composition as claimed in claim 14, wherein, when the painted inhibitor of described composition a urea-carbamate compounds and/or composition b is disperseed, use at least a dispersant that is selected from nonionic or the anionic water-soluble macromolecular compound in polyvinyl alcohol derivative and the cellulose derivative and is selected from the anion surfactant to make its dispersion.
16. composition as claimed in claim 15, wherein, described polyvinyl alcohol derivative is the polyvinyl alcohol of sulfonic acid modified, described cellulose derivative is a hydroxypropyl methylcellulose, and described anion surfactant is to be selected from least a in the slaine of beta-naphthalenesulfonic-acid formaldehyde condensation compound and the poly carboxylic acid derivative's type surfactant.
17. recording materials are provided with the color layer that contains each described composition of claim 1～16 on support.
18. recording materials as claimed in claim 17, wherein, described recording materials are thermal recording mediums.
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